KR102473123B1 - Structure, laminate thereof, manufacturing method and manufacturing apparatus therefor - Google Patents

Abstract

An object of the present invention is to solve the problem that there is no method for inexpensively forming a dense structure on a porous structure. In addition, the present invention solves the problem of providing a laminated body thereof as well as providing a structure made of a high-quality and inexpensive brittle material serving as an intermediate layer that facilitates the formation of a dense structure on a porous structure. The structure is provided with an aggregate of brittle particles including a plurality of brittle particles, the aggregate of brittle particles is provided with a brittle material cross-linked structure region for preventing the brittle particles from moving, and the brittle particles are disposed adjacent to each other and surrounded by the brittle particles. It has a brittle material region along the brittle material region and is bonded together by bridging (connecting) together through the brittle material region.

Description

Structure, laminate thereof, manufacturing method and manufacturing apparatus therefor

One embodiment of the present invention relates to a brittle material structure comprising a brittle particle aggregate in which brittle material fine particles are aggregated, a laminate thereof, and a manufacturing method thereof. In addition, one embodiment of the present invention relates to a structure in which a structure is formed on a substrate by spraying aerosolized fine particles onto a substrate, a manufacturing method thereof, and a manufacturing apparatus thereof.

Structures and laminates of brittle materials such as ceramics, alloy particles, and brittle resins, or laminates using brittle materials as raw materials generally have high hardness and excellent wear resistance, heat resistance, and corrosion resistance. General-purpose industrial devices such as machinery, information devices such as smartphones and PCs, and electronic parts that make up them, automobiles, gas turbines for power generation and jet engines for aerospace, kitchen appliances and home appliances, solar cells, fuel cells, lithium ion batteries, etc. It is used in a wide range of fields, such as energy-related members of the body and medical members such as dentures and implants. However, structures of brittle materials and laminates thereof are generally brittle at room temperature, so it is difficult to process using plastic deformation like metals or plastic resins, and also difficult to cut because of their high hardness. Therefore, when forming a structure of a brittle material or, in particular, a laminate thereof, it is common to mold and sinter the raw material powder or melt it using some thermal energy to produce it in a state that is easy to flow, or to form it in a highly reactive state by miniaturizing it. . For example, as a method of manufacturing a structure of a brittle material, a sintering method or a substitute melting method is known, and as a method of manufacturing the laminate, a gas phase method such as sputtering, physical vapor deposition, and chemical vapor deposition, or a thermal spraying method is known. Representative melting methods, chemical solution methods, printing methods, aerosol deposition methods, and the like are known.

The sintering method or the printing method is a method of producing a brittle material structure by molding submicrometer to micrometer-sized powder particles, which are generally raw materials, as they are or in the form of a paste, and heating and maintaining the temperature below the melting point, which is called the sintering temperature. to be. During this firing, since it is necessary to heat and maintain a high temperature, thermal influence on the surrounding area is unavoidable. It comes with certain restrictions.

Therefore, a thermal spraying method is known as a method of manufacturing a structure or laminate of brittle materials that limits the thermal effect on such heterogeneous members. In the thermal spraying method, the desired brittle material is made into powder particles of several micrometers to several tens of micrometers, put into a thermal plasma or high-speed combustion flame, and sprayed onto a target substrate. At this time, the injected powder particles are exposed to high-temperature and high-velocity thermal plasma or combustion flame, are heated and melted, and are accelerated to collide with the substrate. Particles that have been partially or completely melted by a heating source and become molten droplets are flattened and rapidly cooled upon collision, resulting in pancake-shaped particles called splats with an aspect ratio distorted in the direction of collision. It is the basic unit of stacking and becomes a structure. Therefore, although the thermal spraying method is a good method for producing a thick film structure of a brittle material, since it is a process involving phase transformation of melting and solidification, the crystalline state of the initial raw material cannot be maintained during melting, and cracks occur during rapid cooling and solidification to produce a dense structure. It is difficult to do (for example, Non-Patent Document 1). Therefore, as a study to increase the density of the structure formed by the thermal spraying method, for example, increasing the flight speed of the fine particles compared to the conventional thermal spraying method, or using finer raw material fine particles than those used in the conventional thermal spraying method. Efforts are being made.

On the other hand, techniques such as sputtering or physical vapor deposition for producing a laminate by sublimating raw materials into a vapor state, and chemical vapor deposition for molding while synthesizing a brittle material by a chemical reaction are known. In these techniques, a brittle material as a raw material is sublimated in a gaseous state in a high vacuum state, and particles in a supersaturated state are precipitated and deposited on a substrate to form a structure. Although it is advantageous for forming a dense film, it is difficult to form a thick structure in that the formation speed is generally slow. In addition, when layering at high speed, it is difficult to make a dense film, and a structure in the form of columnar crystals reminiscent of feathers or cauliflower is formed (for example, Non-Patent Document 2). .

Meanwhile, an aerosol deposition method is known as a method of forming a brittle material structure and a laminate thereof by spraying the brittle material in a solid state. In this method, a brittle material as a raw material is made into fine particles of 1 μm or less and sprayed as an aerosol in a vacuum state, using the impact solidification phenomenon at room temperature that can be observed when the particle size is smaller than about 1 μm. , a method for forming a structure of brittle material and a laminate thereof. Although the aerosol deposition method is a very interesting method, it is difficult to obtain a self-supporting structure because it uses a phenomenon that occurs accompanying the collision phenomenon, and it is highly dependent on the surface hardness and smoothness of the other material, and the formation speed is higher than that of the thermal spray method. The fact that is slow can be cited as a problem (for example, Non-Patent Document 3).

On the other hand, a technique called cold spray is known. This method is a lamination method in which particles are plastically deformed and attached by energy at the time of collision, and is an excellent forming method for ductile materials capable of plastic deformation, but is inherently difficult to apply to brittle materials targeted by the present invention. (For example, Non-Patent Document 4).

On the other hand, in the application area of the brittle material mentioned at the outset, as the application field is advanced, the demand for a structure of brittle material such as ceramic material and a laminate thereof is also increasing. For example, in a turbine member of an aircraft jet engine, the problem of damage to the porous thermal barrier coating by vitreous deposits called CMAS included in volcanic ash or sand is becoming serious, and a brittle material structure that prevents the intrusion is required ( For example, non-patent literature 5).

Also in energy-related members such as battery materials, a brittle material structure that also serves as a permeation prevention layer is required as a solid electrolyte in porous electrode materials that are required to pass gas or fuel. Also in medical members, a ceramic structure that is a brittle material for obtaining a smooth surface is required for a porous material such as artificial bone. In addition, even in electrical insulation materials, a ceramic structure, which is a brittle material that secures insulation properties, is required on electrode materials.

Also, as a technology that has recently attracted attention, there is a technology called additive manufacturing technology or 3D modeling technology. This technology is a technology for manufacturing a 3D structure by decomposing a complex 3D structure into a layered structure and stacking them as a 2D laminate. Since the layers are overlapped in this technology, in principle, the occurrence of surface roughness due to the level difference between the layers is a problem. In the case of resin or metal, post-processing is relatively easy, but ceramic 3D modeling is difficult to post-process because of its high hardness.

Summarizing these common problems, forming a dense structure of brittle materials for the purpose of prevention of penetration of penetrating components or electrical insulation on a porous structure for the purpose of permeation of fluid substances such as gas and thermal shock resistance is an urgent need to be solved. It is a task. However, in reality, it is difficult to cheaply and easily form a dense structure on a porous structure by the above-mentioned means.

For example, in the thermal spraying method, a thick film structure of a brittle material can be formed on a porous structure. However, the thick film structure usually contains cracks due to rapid solidification, so that a dense structure cannot be obtained. To solve this problem, a method of glazing the deposited thermal sprayed coating with a laser can be cited (for example, Non-Patent Document 6). However, since phase transformation is inherently involved in laser glazing, cracks are introduced due to contraction during rapid solidification and cooling, and a structure with high density can be obtained locally, but the sealing function cannot be sufficiently exhibited as a whole.

In the aerosol deposition method, fine particles are aerosolized, and the aerosol is sprayed from a nozzle at high speed at room temperature and reduced pressure on a substrate, and the collision pressure caused by collision between the particles or between the particles and the substrate due to the kinetic energy of the particles is used, and has no thermal history. method to obtain a dense structure that does not Since the aerosol deposition method can deposit a brittle material without phase transformation, a dense brittle material structure can be fabricated. However, when laminated on a porous structure, there is a problem in that the pore portion is piled up by spraying, that is, the powder is piled up, and a compressed powder body is formed at the pore position. For this reason, it is difficult to laminate a dense brittle material structure on a porous structure by an aerosol deposition method.

On the other hand, a structure formed by a conventional aerosol deposition method has a dense bonding region between fine particles that is uniform and does not contain an amorphous phase or the like. In the structure formed by the conventional aerosol deposition method, high adhesion between the particles and the substrate is ensured by a structure called an anchor layer formed on the substrate when the particles collide with the substrate, by penetration of the particles into the substrate. In a vapor deposition method typified by an aerosol deposition method in which ultrafine particle materials are accelerated and deposited by colliding with a substrate, a method of irradiating ultrafine particles or a substrate with a high-energy beam to activate the particles has been proposed.

In Patent Document 1, ultrafine particles or a substrate are irradiated with high-speed, high-energy beams such as high-energy atoms or molecules such as ion, atom, and molecular beams or low-temperature plasma to remove contamination layers and oxide layers without melting or decomposing ultrafine particle materials. It is activated by amorphization or amorphization, and realizes a strong bond between ultrafine particles and a substrate or between ultrafine particles in a low-temperature state even if they collide at a low speed. A method of forming is disclosed.

Patent Document 2 discloses a method of irradiating a high-energy beam before ultrafine particles reach a substrate. It is said that it is effective to make irradiation energy into 1 kW or less especially.

In Patent Document 3, there is a method of forming a structure on the surface of a substrate by performing energy irradiation to remove impurities from the surface of brittle material particles in a reduced pressure atmosphere, aerosolizing fine particles from which impurities have been removed, and colliding them to crush and deform the particles. It is proposed.

In all of Patent Literature 1 to Patent Literature 3, there is no specific description of the structure, so it is clear that a specific structure is not an intended invention. In addition, since the target material is also a substrate and the plate-shaped counterpart material is the target, it is considered that the laminate structure is also intended to be laminated on a flat material, and it is clear that the purpose is not to form a dense structure on a porous structure. .

From the above, it can be seen that it is generally difficult to laminate a dense structure on a porous structure. In addition, by any method, it is based on obtaining a dense structure while maintaining the crystallinity of the raw material particles, and practical mechanical strength, homogeneity, and large-area thick film formation could not be realized at the same time while maintaining a practical film formation speed and utilization efficiency of the raw material powder. .

Patent Document 1: Japanese Unexamined Patent Publication No. 2001-247979 Patent Document 2: Japanese Unexamined Patent Publication No. 2000-212766 Patent Document 3: Japanese Unexamined Patent Publication No. 2008-88559

Non-Patent Document 1: H. Herman, Scientific American 259 [3] (1988) 112-117 Non-Patent Document 2: J.A. Thornton, Annual Review of Materials Science 7 (1977) 239-260 Non-Patent Document 3: J. Akedo, Journal of the American Ceramic Society 89 [6] (2006) 1834-1839 Non-Patent Document 4: A. Papyrin et al., Cold spray technology, Elsevier (2006) Non-Patent Document 5: J. M. Drexler et al., Advanced Materials 23 (2011) 2419-2424 Non-Patent Document 6: C. Batista et al., Surface and Coatings Technology 200 [24] 6783-6791

One problem to be solved by the present invention is that there is no method for inexpensively forming a dense structure on a porous structure. Another object of the present invention is to provide a high-quality and inexpensive brittle material structure and a laminate thereof as an intermediate layer for facilitating formation of a dense structure on a porous structure.

On the other hand, in the conventional thermal spraying method and the thermal spraying method conducted in the above-mentioned research, since the formed brittle material structure melts the entire microparticles and uses the material flow by heat, the interface where the brittle material microparticles in the structure are joined , due to rapid melting and condensation, a large number of pores or voids due to poor gas-liquid substitution are included. In addition, it is difficult to form a homogeneous and dense structure because cracks are generated in the structure during rapid melting and solidification. In addition, the structure formed by the conventional thermal spraying method includes a layered structure representing a pancake-shaped particle shape called splat, which has a distorted aspect ratio in the direction of collision, because the brittle particles in the state of molten droplets are flat and rapidly cooled upon collision. Therefore, it is difficult to form a structure having an isotropic structure. In addition, in the conventional thermal spraying method, when the raw material fine particles are re-solidified, for example, even though Al ₂ O ₃ particles composed of only α phase are formed as a starting material, they are transformed into Al ₂ O ₃ containing γ phase in the structure, etc. Since the crystal structure of the raw material fine particles is accompanied by crystal phase transformation, the original crystal structure of the raw material fine particles cannot be maintained, and the functionality derived from the raw material fine particles from which the structure is obtained is reduced.

In the conventional aerosol deposition method, since the material flow due to the collision pressure generated by the collision between the particles or between the particles and the substrate is used, the crystal structure of the raw material particles is maintained and a dense structure is formed. The area of the active surface that contributes to the bonding between the particles or between the particles and the substrate on the surface of the particles to be formed becomes small, and as a result, the efficiency of using the particles of the raw material is lowered, and the speed of forming the structure is not as high as that of the spraying method, so that large structures, etc. Its intended use lacked practicality.

Furthermore, as a problem common to the conventional thermal spraying method and the conventional aerosol deposition method described above, there is a limit to the shape or material of the substrate that can be used for the structure. For example, a thermoplastic resin substrate suffers from large thermal damage to the substrate in the conventional thermal spraying method, while the impact pressure required to form a bonding region is small in the aerosol deposition method, making it difficult to obtain a structure in both cases. In addition, even if a structure can be obtained, in order to ensure adhesion between the substrate and the fine particle bonding area, irregularities are attached to the substrate surface in the conventional thermal spraying method, the substrate surface is smoothed in the conventional aerosol deposition method, or other raw material fine particles It requires a pretreatment step for the base material, such as attaching a ground layer made of a different material. From the above, in the conventional method, it is generally difficult to form a structure that retains the characteristics of the raw material fine particles, regardless of the material or shape of the base material.

Therefore, another object of the present invention is a crystal that does not cause thermal or physical damage to the particles or substrate forming the structure, maintains the characteristics and functions of the particles as a raw material, and has excellent mechanical and electrical properties and good coating and adhesion. to form a structure. In addition, another object of the present invention is a crystal that does not cause thermal or physical damage to the particles or substrate forming the structure, maintains the characteristics and functions of the particles as a raw material, and has excellent mechanical and electrical properties and good coating and adhesion. It is to provide a method for forming a film of a structure. In addition, another object of the present invention is a crystal structure that does not cause heat or physical damage to the particles or substrate forming the structure, maintains the characteristics and functions of the particles as a raw material, and has excellent mechanical and electrical properties and good coating and adhesion. It is to provide a film forming device of

According to one embodiment of the present invention, a structure comprising brittle particle aggregates having a plurality of brittle particles, wherein the brittle particle aggregates are disposed adjacent to each other, and the brittle particles having a brittle material region around the brittle material region Provided is a structure characterized by having a brittle material crosslinked structure region that bonds between the brittle particles and prevents the brittle particles from moving by being crosslinked (connected) by a.

In one embodiment of the present invention, the brittle material crosslinked structure region may have a three-dimensional network structure between brittle particles.

In one embodiment of the present invention, the brittle material cross-linked structure region may be particularly amorphous.

In one embodiment of the present invention, the brittle material cross-linked structure region may be substantially uniform on the surface of the brittle particle.

In one embodiment of the present invention, the brittle material crosslinked structure region may have voids.

In one embodiment of the present invention, the thickness of the brittle material crosslinked structure region may be 100 nm or less.

In one embodiment of the present invention, the brittle material crosslinked structure region may be composed of the same elements as those of the brittle particles.

In one embodiment of the present invention, the size of the brittle particles may be less than 5 μm.

In one embodiment of the present invention, the hardness of the structure may be greater than or equal to 0.1 and less than 1 relative to the hardness of the brittle particles.

A laminated structure in which a structure according to an embodiment of the present invention is disposed on a substrate is provided.

In one embodiment of the present invention, the brittle particles may have a flat shape perpendicular to the substrate.

In one embodiment of the present invention, the substrate may be a porous body.

In one embodiment of the present invention, the microparticles may have a crystallite size of 1 nm or more and 300 nm or less after deformation.

In one embodiment of the present invention, the structure may have 0.02<internal compressive stress/Vickers hardness<0.5.

In one embodiment of the present invention, the value of the short/long side of the fine particle may be the value of the fine particle near the interface of the substrate > the value of the fine particle near the surface layer of the structure.

In one embodiment of the present invention, the structure may have an insulation withstand voltage of 20 kV/mm or more in either direct current or alternating current measurement.

In addition, in one embodiment of the present invention, agglomerated particles in which primary particles are agglomerated among the raw material fine particles are pulverized into primary particles, and the surface of the primary particles is activated to generate an active region, and a plurality of the active regions are provided. Provided is a method for manufacturing a structure in which the primary particles having a plurality of the active regions are bonded through the active regions by ejecting the primary particles to a substrate.

In one embodiment of the present invention, in the manufacturing method of the structure, an active region may be formed on the surface of the primary particle by a collision crushing effect of the primary particle and a thermal effect of plasma.

In addition, in one embodiment of the present invention, an aerosol generator, a grinder, a plasma generating device, and a nozzle connected to the plasma generating device are provided, the grinder is installed in front of the plasma generating device, and the grinder Provided is a structure manufacturing device that pulverizes agglomerated particles in which primary particles transported from the aerosol generator are agglomerated and transports them to the plasma generating device.

By using the structure according to one embodiment of the present invention, a desired crystalline brittle material structure can be easily obtained. That is, according to the embodiment of the present invention, since it is possible to provide a high-quality, inexpensive brittle material structure and a laminate thereof, the free energy is higher than or equal to that of brittle material particles, which are the main phase, named the brittle material crosslinked structure region. A brittle material structure intermediate between a porous structure and a dense structure can be manufactured by adopting a structure in which brittle material particles in a columnar shape are connected by brittle material regions in the state.

Since the brittle material structure according to one embodiment of the present invention has low anisotropy, it can be formed on a surface having a complicated shape. At this time, since the Gibbs free energy is in a high state, the three-dimensional network structure according to one embodiment of the present invention is in an active state, so it can be formed with high adhesion on the porous structure. In addition, since the brittle material structure according to an embodiment of the present invention takes a three-dimensional network structure of brittle materials, the structure itself has a function of improving encapsulation performance. In addition, since the smoothness of the surface is high, it is possible to laminate a dense brittle material on the surface, and it can have a sealing function as a laminate. In this regard, the brittle material structure according to one embodiment of the present invention can also be used as a structure serving as an intermediate bonding layer for bonding a porous structure and a dense structure. In addition, since the brittle material structure according to an embodiment of the present invention may have meso-scale pores embedded in the three-dimensional network structure, mechanical and thermal properties such as the apparent elastic modulus and thermal conductivity of the structure may be controlled. This is advantageous in that cracks such as long-period cracks are prevented and deterioration in the sealing function of the structure is prevented. In addition, as a secondary effect, since the brittle material structure according to one embodiment of the present invention has excellent stacking ability from its structure, it can be formed faster than a structure manufactured by a conventional brittle material structure manufacturing process. Therefore, it can be manufactured inexpensively and simply.

In addition, according to an embodiment of the present invention, the structure can be formed without heat and physical damage to the substrate forming the structure. In addition, since the crystal structure of the raw material microparticles is maintained, it is possible to form a dense structure maintaining the characteristic functions of the microparticles. In addition, by having the structural features of the present invention in the bonding area between the microparticles and the bonding area between the microparticles and the substrate in the structure, a structure having excellent mechanical and electrical properties and excellent covering properties and adhesion can be formed. In addition, according to one embodiment of the present invention, a manufacturing method capable of forming a structure without causing heat and physical damage to a substrate forming the structure is provided. In addition, according to one embodiment of the present invention, a manufacturing apparatus capable of forming a structure into a film without heat and physical damage to a substrate forming the structure is provided.

1 is a schematic diagram of a brittle fine particle aggregate according to an embodiment of the present invention.
2 is a schematic diagram of a brittle fine particle aggregate according to an embodiment of the present invention.
Fig. 3 is a configuration explanatory diagram of an apparatus 10 for forming an ultra-fine particle structure for a plasma source used for forming a brittle material structure according to an embodiment of the present invention.
4 is a scanning transmission electron microscope image of a cross-section of a structure obtained according to an embodiment of the present invention and a mapping diagram of electron energy loss spectroscopy. (a) is an annular dark-field image by a scanning transmission electron microscope. (b) is the mapping result of α-alumina by electron energy loss spectroscopy, (c) is the mapping result of γ-alumina by electron energy loss spectroscopy, (d) is the mapping result of amorphous alumina by electron energy loss spectroscopy .
5 is an X-ray diffraction result of a raw material particle, a structure (argon gas), and a structure (helium gas) according to an embodiment of the present invention.
Figure 6 (a) is a scanning electron microscope image of the cross section of the raw material alumina powder. Figure 6 (b) is an enlarged image of the dotted line area in (a).
7 is a transmission electron microscope image of a cross section of an alumina thermal sprayed coating.
8 is a transmission electron microscope image of a cross section of a structure according to an embodiment of the present invention.
9 is a transmission electron microscope image of a cross section of a structure according to an embodiment of the present invention.
10 is a scanning electron microscope image of a cross-section of a laminate according to an embodiment of the present invention.
11 is a cross-sectional model of a structure 1100 according to an embodiment of the present invention.
12(a) is a cross-sectional model of a structure 1200 according to an embodiment of the present invention. 12(b) is a cross-sectional model explaining details of the fine particles 1201 having a modified surface shape formed by being deposited on a substrate 1204. As shown in FIG.
13 is a cross-sectional model of a structure 1300 according to an embodiment of the present invention.
14(a) is an enlarged view of a bonding area between particles of a structure 1100 according to an embodiment of the present invention, and (b) is an enlarged view of a junction area between particles of a structure 1200 according to an embodiment of the present invention. It enlarges the junction area.
In (a) of FIG. 15 , single crystal fine particles 1010 are represented as hexagonal single crystals, (b) are represented as hexagonal polycrystalline fine particles 1021 having crystallites 1022, and (c) are hexagonal polycrystalline fine particles having crystallites 1032. Reference numeral 1031 denotes agglomerated powder 1030.
16 (a) shows the raw material particulate 1501 used to form the structure according to an embodiment of the present invention, and (b) shows the small deformed particulate constituting the structure according to an embodiment of the present invention. (1101), and (c) shows a particle 1201 having a large deformation among the structures according to an embodiment of the present invention.
17 is a schematic diagram of an apparatus 2000 for manufacturing a structure according to an embodiment of the present invention.
18 is a diagram illustrating a method for manufacturing a structure according to an embodiment of the present invention.
19 (a) is a cross-sectional model of collision and crushing deformation of raw material particles 1041 by a conventional aerosol deposition method, and (b) is a model of collision and crushing of raw material particles 1041 by a manufacturing method according to an embodiment of the present invention. It is a cross-sectional model that is deformed.
20(a) is a cross-sectional model of bonding between particles and bonding between particles/substrate by a conventional aerosol deposition method, and (b) is a cross-sectional model of bonding between particles and bonding between particles/substrate by a manufacturing method according to an embodiment of the present invention. It is a combined cross-section model.
21 (a) shows a scanning transmission electron microscope image of the particulate according to an embodiment of the present invention, and (b) shows a mapping diagram of electron energy loss spectroscopy.
22 shows a surface observation image using raw material particles according to an embodiment of the present invention.
23 (a) shows α-Al ₂ O ₃ used as a starting material according to an embodiment of the present invention, and (b) shows a cross-sectional transmission electron microscope image of a structure according to the present invention formed using fine particles. As a comparison, (c) shows a cross-sectional transmission electron microscope image of a structure formed by an aerosol deposition method using starting materials.
24 (a) shows a cross-sectional SEM image of a structure 1600 according to an embodiment of the present invention, and (b) shows a cross-sectional SEM image of a structure 1700 according to an embodiment of the present invention.
25 shows an X-ray diffraction pattern of a structure 1600 according to an embodiment of the present invention.
26 shows an X-ray diffraction pattern of a structure 1700 according to an embodiment of the present invention.
27 shows X-ray diffraction patterns of the structures obtained in Examples 9 and 10.
28 shows the utilization efficiency ratio of raw material particulates according to an embodiment of the present invention.
29 shows the utilization efficiency ratio of raw material particulates according to an embodiment of the present invention.
30 shows a cross-sectional image of a structure 1800 using a porous ceramic as a substrate 1804 according to an embodiment of the present invention by a scanning transmission electron microscope, and (b) is an enlarged view of (a).
Figure 31 (a) shows the result of using a cellophane tape for masking according to an embodiment of the present invention, (b) shows the result of using a polyimide tape for masking according to an embodiment of the present invention.
32 (a) to (e) show a structure according to an embodiment of the present invention, and (f) shows a structure using a substrate having a curved shape according to an embodiment of the present invention.
33 is a photograph of a structure using a ceramic porous substrate according to an embodiment of the present invention.
34(a) is an image of a fracture surface of a structure according to an embodiment of the present invention observed by FE-SEM, and (b) is an enlarged observation image of the vicinity of the substrate interface 3114 of (a), (c) is an enlarged observation image of the vicinity of the surface layer 3113 in (a).
35 is a cross-sectional model of an inclined structure 3100 according to an embodiment of the present invention.
36 is a diagram showing the relationship between the thickness and withstand voltage of a structure according to an embodiment of the present invention manufactured using argon gas (gas flow rate: 20 L/min).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a structure according to the present invention, a laminate thereof, a manufacturing method and a manufacturing apparatus thereof will be described with reference to the drawings. In addition, the structures of the present invention, their laminates, and their manufacturing methods and manufacturing apparatuses are not construed as being limited to the descriptions of the embodiments and examples described below. In the drawings referred to in this embodiment and the examples described later, the same reference numerals are assigned to the same parts or parts having similar functions, and repeated explanations are omitted.

The present inventors predicted that if the dense structure and the porous structure can be connected and the intermediate structure can be inexpensively manufactured, the dense structure can be laminated on the porous structure through the intermediate structure. In addition, it was predicted that if a dense structure can be laminated on a porous structure, the application range of brittle materials such as ceramics and alloy materials can be greatly expanded, contributing to industrial development. Therefore, if a ceramic structure film capable of smoothing this level difference can be applied to the surface, it greatly contributes to the realization of a three-dimensional molding technology for ceramics.

[brittle material cross-linked structure area]

In the present invention, in order to provide a high-quality, inexpensive brittle material structure and a laminate thereof, a brittle material region in a state equal to or higher in free energy than the main phase brittle material particles, named a brittle material crosslinked structure region, By adopting a structure in which brittle material particles in a columnar shape are connected by means of a porous structure, a brittle material structure intermediate between a porous structure and a dense structure can be produced. More specifically, it is a structure comprising a brittle material particle aggregate having a plurality of brittle material particles, wherein the brittle material particle aggregates are disposed adjacent to each other and have a brittle material region around the brittle material particles, By cross-linking (connecting) by the material region, the brittle material particles are bonded to each other and the movement of the brittle material particles can be prevented, so that a stable structure can be formed. It is possible to more easily obtain a cross-linked structure by combining these brittle material regions while maintaining a higher free energy than brittle material particles. After this bonding, since the bonding state is quenched and maintained, as a result, the free energy of the brittle material crosslinked structure region becomes higher than or equal to the free energy of the brittle material particles. As such a state, an amorphous state is mentioned, for example. It was found that the above problems can be solved by using a structure according to an embodiment of the present invention. 1 and 2 show schematic diagrams when viewing a cross section of a brittle material particle aggregate according to an embodiment of the present invention. See Figure 1. A plurality of brittle material particles 102 and a brittle material crosslinked structure region 101 present on the surface of the brittle material particles 102 exist, and the brittle material crosslinked structure region 101 exists between neighboring brittle material particles 102 A cross-linked (connected) form is schematically expressed through. Gaps 103 exist between the brittle material particles 102 .

2 is an enlarged view of a portion of the crosslinked structure 104 and the same portion. See Figure 2. Brittle material particles 105, brittle material particles 106, and a brittle material cross-linked structure region 107, which is a region having an amorphous structure, exist, and the brittle material particles 105 and brittle material particles 106 have an amorphous structure. A crosslinked (connected) form is schematically represented by the brittle material crosslinked structure region 107 as a region. 1 and 2 are two-dimensional representations of a three-dimensional cross-linked state, and in fact, brittle material particles are further present on the back side of the page of FIG. 1 or the back side of the page of FIG. 2, and the brittle material cross-linked structure region is a three-dimensional network take a rescue In addition, although the brittle material crosslinked structure region appears to exist all around the brittle material particle in the figure, it is not necessarily limited to such a structure, and it is sufficient as long as the brittle material crosslinked structure region exists in at least a part around the brittle material. It is preferable that the brittle material cross-linked structure region exists all around the brittle material. In addition, amorphous means that the constituent elements do not have long-term periodicity and are in an amorphous state. The ratio of metal elements to non-metal elements such as oxygen, nitrogen, carbon, boron, and fluorine It can also be defined in a state different from the ratio with non-metal elements such as carbon, boron, and fluorine.

The degree of freedom of the structure can be increased because the brittle material crosslinked structure region takes a three-dimensional network structure. Also, since the brittle material region uniformly covers the surface of the brittle material particles, adhesion between the brittle material particles may be improved. At this time, if the thickness of the brittle material region is 100 nm or less, it is preferable because the ratio of brittle material particles to the brittle material crosslinked structure region can be relatively increased.

[Definition of brittle material]

In this specification, a brittle material refers to a material from which ductile deformation or plastic deformation is difficult to expect when fabricating a structure at around room temperature, and generally refers to a material that is difficult to plastic process. Examples thereof include ceramics such as oxides, nitrides, carbides, borides and fluorides, glass, intermetallic compounds, high molecular polymer materials, and semiconductors such as silicon.

[Definition of Brittle Material Particles]

In this specification, brittle material particles refer to particles composed of the brittle material and have an average particle diameter of 5 μm or less as identified by particle size distribution measurement or scanning electron microscopy. An average particle diameter of 5 μm or less is preferable because the uniformity of the structure can be improved. In particular, if the size of brittle material particles is less than 1 μm, the uniformity of the structure can be further increased, and encapsulation performance and surface smoothness can be improved, which is preferable. At this time, the columnar brittle material particles become isotropic, which increases the degree of freedom of the structure and facilitates the formation of the structure on the three-dimensional substrate. For example, it is preferable that the ratio of the major axis to the minor axis of the particles is 5 or less. Also, in this specification, brittle material particles are sometimes referred to as brittle particles or fine particles.

[air gap]

Further, the structure according to one embodiment of the present invention is superior in that the effective elastic modulus and hardness of the brittle grain aggregate structure can be controlled by forming a void in the brittle material crosslinked structure region. At this time, the sealing property can be improved by setting the void to at least 1 μm or less. At this time, it is preferable to set the Vickers hardness of the brittle material structure to 0.1 or more with respect to the Vickers hardness of the columnar brittle particles because the strength of the structure can be maintained. At this time, by adjusting the Vickers hardness of the brittle material structure to be less than 1 with respect to the Vickers hardness of the columnar brittle particles, it is possible to make the structure excellent in compliance with the requirements. If it is difficult to measure the Vickers hardness of brittle material particles, the Vickers hardness of a dense bulk structure prepared by sintering brittle material particles may be used as a standard. Vickers hardness was given as an example, but similar evaluation can be made by other mechanical property values such as effective elastic modulus, thermal conductivity, and electrical property values such as impedance measurement. By adjusting the effective elastic modulus to be less than 1 with respect to the elastic modulus of the columnar brittle particles, it is possible to obtain a structure that satisfies the required specifications, which is preferable. At this time, by setting it to 0.01 or more, it is preferable because the strength as a structure can be maintained. Since the brittle material structure according to one embodiment of the present invention can excellently comply with the requirements, it is particularly effective as a high-temperature encapsulation material excellent in thermal shock.

[Constituent Elements]

It is preferable from the viewpoint of stability that the brittle material structure region is composed of the same elements as the brittle particles. In particular, when the brittle particles are composed of two or more types of metal elements, it is preferable from the viewpoint of stability that the composition ratio of the metal elements is the same or substantially the same.

Since the brittle material structure according to an embodiment of the present invention has a brittle material crosslinked structure region, the modulus of elasticity can be adjusted, and it is easy to form on a three-dimensional surface, so that various substrates such as metals, ceramics, polymers, and composite materials can be used. It is easy to form in This works particularly effectively when the base material is a porous material such as a thermal spray coating, and can maintain the sealing function.

It can also be used as an intermediate layer, and by forming a brittle material structure according to an embodiment of the present invention on a porous substrate and producing a dense structure thereon, it is possible to further improve the sealing function. At this time, by adding the assistance of the collision energy, the brittle material particles can be made into a flat shape perpendicular to the substrate, and further improvement in encapsulation can be expected.

[Method for manufacturing structure]

A structure according to one embodiment of the present invention can be manufactured by, for example, laminating brittle material particles whose surface is activated by plasma. At this time, more specifically, high energy such as plasma or laser is uniformly irradiated around the columnar brittle material particles of several μm or less. By setting the surface of the brittle material particle in an activated state while suppressing the center of the brittle material particle to a phase transformation temperature or less, a phase with high activation degree is uniformly precipitated on the surface of the brittle material particle by energy irradiation. At this time, since the properties of the plasma and the laser irradiation field remain in a state in which the property as a fluid remains, it can be used as an acceleration source for brittle material particles, and by colliding and stacking these highly active particles, The material regions react with each other to form a three-dimensional network. At this time, the brittle material particles, which are the main phase, maintain their raw material state and can maintain the initially combined crystalline phase. In addition, by passing brittle material particles through a plasma having a high electron temperature in a state in which a property as a thermal fluid is further imparted, it is easy to collide with the surface in an activated state while suppressing the central portion to a phase transformation temperature or less, which is preferable.

3 is a schematic diagram of an apparatus used to form a brittle material structure according to an embodiment of the present invention. This apparatus has a film formation chamber (111). A nozzle 112 is installed in the film formation chamber 111 . A coil 113 for flowing current is installed in the nozzle 112 to generate high-frequency plasma. Further, a vacuum pipe 114 and a vacuum pump 115 are connected to the film formation chamber 111 . The nozzle 112 is connected to an aerosol generating device 116 installed outside the film formation chamber 111 through a transport pipe 117 for transporting ultrafine particles. In addition, a pressure gauge 118 for measuring pressure is installed in the deposition chamber 111 . The inside of the film formation chamber 111 is depressurized by the vacuum pipe 114 and the vacuum pump 115, and the pressure during film formation is read by the pressure gauge 118. A substrate 119 is installed in the deposition chamber 111 . Substrate 119 may be fixed or displaced relative to nozzle 112 .

A brittle material structure is formed through the following operation using the device constructed as described above. The vacuum pump 115 is operated to put the inside of the deposition chamber 111 in a reduced pressure state via the vacuum pipe 114 . In this state, inductively coupled high-frequency plasma is generated in the nozzle 112 by flowing a gas such as helium or argon through the nozzle 112 and flowing a current through the coil 113 . In addition, the aerosol generating device 116 is operated to aerosolize ultrafine particles, which are brittle material particles 120 as a raw material, to generate ultrafine particle aerosol. The generated ultrafine particle aerosol is delivered to the nozzle 112 through the conveying tube 117. In the transported ultrafine particle aerosol, the surface of each particle is activated by the inductively coupled high-frequency plasma of the nozzle 112 to become surface-activated ultrafine particles 121 . The surface-activated ultrafine particles 121 are introduced into the depressurized deposition chamber through the nozzle 112 and sprayed onto the substrate 119 . The sprayed surface-active ultrafine particles 121 are deposited on the substrate 119, and the surface-active surfaces of the ultrafine particles are strongly bonded to each other to form a three-dimensional network of surface-active brittle structures. At this time, since the original surface-active portion exists on the surface of each ultrafine particle, it becomes a three-dimensional network surface-active structure having brittle material particles in the surface-active three-dimensional network. In addition, voids are also generated in the surface active three-dimensional network, and the amount of voids can be controlled according to the filling degree of the brittle material particles. At this time, it may also have a structure in which pores are filled with a surface active material. By using helium as the plasma gas, it is possible to form a dense structure with a higher degree of filling compared to the case of using argon gas.

In this case, inductively coupled high-frequency plasma was used as the particle activation source, but DC plasma may also be used. Also, it does not matter if a capacitively coupled high-frequency plasma is used. It is important to maintain the electron temperature of the plasma in a high state, while maintaining the properties of the plasma gas as a fluid or thermal fluid, so that it becomes a source of acceleration or heating acceleration of brittle material particles.

Although an example of an aerosolization method has been introduced as an input form of the brittle material fine particles, a suspension form in which the fine particles are dispersed in a solvent is also acceptable.

By adding the assistance of impact energy when forming the brittle material structure region according to one embodiment of the present invention, the cooperation of room temperature impact solidification can be added, and a more dense structure can be obtained. At this time, the brittle material particles become a flat shape perpendicular to the substrate. Since the deformation of the brittle material particles is the deformation of the solid particles, the aspect ratio of the flatness is small compared to the flatness of the molten droplet as seen in the thermal spraying method. When brittle material grains are deformed, crystallite size refinement is accompanied. In addition, when forming the brittle material structure region according to an embodiment of the present invention, an inclined structure in which the amount of voids is reduced upward may be formed by relatively increasing the amount of assistance from collision energy.

When forming the brittle material structure region according to an embodiment of the present invention, cooperation in a semi-molten state can be added by adding the assistance of thermal energy, thereby increasing the degree of freedom of three-dimensional formation.

On the other hand, in view of the above-mentioned problems of the conventional method, only the extreme surface layer of the fine particles or substrate is bonded to each other or between the fine particles and the substrate to the extent that thermal history is not applied to the fine particles or substrate used for the structure. When the fine particles or the fine particles and the substrate are bonded in an easy state, and a compressive stress is applied to the joint region, a dense structure maintaining the crystal structure of the raw material fine particles, which is a problem of the conventional thermal spraying method, can be formed. In addition, it is possible to increase the efficiency of the use of fine particles of raw materials and to speed up the formation of structures, which are problems of the existing aerosol deposition method. In addition, when the fine particles are bonded to each other or between the fine particles and the substrate, good coating properties and adhesion are ensured not only between the fine particles but also between the fine particles and the substrate without being restricted by the material or shape of the substrate. In addition, by forming a dense structure regardless of the material or shape of the substrate, it is possible to greatly expand the application range of brittle materials such as ceramics and alloy materials, thereby contributing to industrial development.

In one embodiment of the present invention, in order to solve the above-mentioned problem, heat and physical damage to the raw material fine particles or substrate is not applied, for example, within the range of not dissolving the raw material fine particles, between the fine particles or between the fine particles and the substrate. It has been found to create active regions in the extreme surface layer of the particulate and substrate, which promote bonding of Furthermore, it has been found that a structure having a compressive residual stress can be formed by applying compressive stress to a junction region through an active region to be created. Preferably, a uniform, homogeneous, and dense structure with compressive residual stress exhibiting an isotropic structure maintaining the crystal structure of the raw material fine particles can be formed by uniformly applying a compressive stress to the joint area.

More specifically, a high-speed, high-energy beam, which is a high-energy atom or molecule such as ion, atom, or molecular beam or low-temperature plasma, is irradiated to the extreme surface layer of the above-mentioned fine particles or substrate to prevent complete dissolution or decomposition of the raw material fine particles and substrate. and a surface active region in which a contamination layer or an oxide layer due to particles or water molecules attached to the surface of a substrate is removed. At the same time, the collision pressure between the fine particles and between the fine particles and the substrate promotes the miniaturization of the crystallite size by crushing the raw material fine particles, and forms a surface active region by the crushed particles. Then, fine particles having a surface active region including fine particles of the raw material are bonded by material flow, so that densification of the enclosing portion of the structure is realized.

The surface of the fine particle and the surface of the substrate, which maintain almost the crystal structure of the raw material fine particles and are easily bonded, are adjacent to each other by collision pressure, thereby creating a bonded region bonded through the surface active region between the particles and between the fine particles and the substrate. form on In addition, the bonding region includes an active region in which the crystal structure is disturbed or the surface of the fine particle is melted by electronically exciting the surface layer of the fine particles or substrate, and the thickness of the bonding region including the active region is 30 nm. It becomes below. In addition, although the mechanical strength of the bond between the crystal grains in which the active region is formed at the joint between the fine particles is reduced, the crystal grain itself is refined by the collision pressure, so that a large number of dislocations are introduced into the crystal grain, and high compressive residual stress can be formed in the structure. As a result, high mechanical strength can be obtained as a whole structure.

The bonding region between the fine particles or between the fine particles and the base material contains elements constituting the raw fine particles or the base material, and depending on the type of the raw fine particle forming the joining region, the type of the base material, or the combination of the fine particles and the base material, for example, The fine particles or the fine particles and the substrate are bonded by chemical bonds such as covalent bonds and ionic bonds. Since the above-described active region is provided only to the extreme surface layer of the raw material fine particles or the extreme surface layer of the base material, as a result, a structure having the above-described bonding region and maintaining the crystal structure of the raw material fine particles can be formed.

Here, a brittle material in this specification refers to a material from which ductile deformation or plastic deformation is difficult to expect when fabricating a structure at around room temperature, and generally refers to a material that is difficult to plastic work. Examples thereof include ceramics such as oxides, nitrides, carbides and borides, glass, intermetallic compounds, and semiconductors such as silicon. In this specification, a substrate is a brittle material, a metal, a polymer, and a porous material of these materials. In addition, when referring to raw material fine particles in this specification, it can be applied not only to brittle material particles such as ceramic fine particles, but also to metal fine particles, high molecular polymer fine particles, and the like.

In the obtained structure, even if crystallites are miniaturized by impact pressure on the microparticles, enlargement of the crystallites by heat cannot occur, so the volume of the microparticles after deformation has the volume of the microparticles as the starting material. After deformation, the crystallite size of the microparticles ranged from 1 nm to 300 nm. By imparting compressive residual stress to the structure, the bonding area of the fine particles is strengthened, and the hardness range of the structure is Hv200 or more and Hv1500 or less in terms of Vickers hardness.

Here, the total energy required to form the structure is defined as the surface activation energy of the active region imparted to the extreme surface layer of the fine particles generated by electronic and/or thermal exposure to plasma and the kinetic energy of the above-described fine particles. . The above-mentioned surface activation energy of the fine particles is energy used for bonding between the fine particles or promoting the bonding through an active region including an amorphous phase. As for the above-mentioned kinetic energy of the fine particles, dislocation is introduced into the crystal grains by impact fracture (crystal refinement) of the fine particles, and compressive residual stress is applied to the bonding between the fine particles, thereby enhancing the bonding between the fine particles and between the fine particles and the substrate. is the energy that In the structure to which the compressive residual stress is applied according to the present invention, the numerical value calculated by taking the internal stress of the structure as the numerator and the mechanical strength (Vickers hardness) of the covering part of the structure as the denominator is defined as a numerical value representing the bonding strength of the fine particles. The mechanical strength or compressive stress of the above-mentioned coating part is affected by the substrate forming the structure, and since both the numerator and denominator described above include the influence, the defined value is a numerical value reflecting the bonding strength of the fine particles. In the structure according to one embodiment of the present invention, 0.02<internal compressive stress/Vickers hardness, preferably 0.02<internal stress/Vickers hardness<0.5. At this time, the Vickers hardness can be obtained in terms of MPa, for example. The compressive residual stress can be estimated from, for example, an X-ray diffraction peak shift.

11 is a cross-sectional model of a structure 1100 according to an embodiment of the present invention. The structure 1100 includes a substrate 1104 and fine particles 1101 having a modified surface shape formed by being deposited on the substrate 1104, and the fine particles 1101 have an active region 1103 including an amorphous phase. It combines with the adjacent particle 1101 with a bonding area. The structure 1100 is obtained when, for example, a large amount of kinetic energy is used in the ratio between the surface activation energy of the fine particles 1101 and the kinetic energy of the fine particles 1101 .

By increasing the ratio of kinetic energy among the energies required to form the structure 1100, material flow accompanied by refinement of the raw material particles proceeds, and a dense structure is obtained. Further, in the structure 1100 obtained by increasing the ratio of kinetic energy, dislocations are introduced into the crystal grains by collision fracture (crystal refinement) of the fine particles 1101, and high compressive residual stress is applied to the junction between the fine particles 1101. By applying, a high-density structure 1100 in which bonding between the particles 1101 is strengthened is obtained. The fine particles 1101 included in the structure 1100 cause collision crushing (crystal refinement) by the fine particles serving as the starting material to generate crystallites 1102 inside the fine particles 1101 . That is, the fine particle 1101 is composed of a plurality of crystallites 1102. In addition, the fine particles 1101 are also accompanied by deformation due to high compressive stress.

12(a) is a cross-sectional model of a structure 1200 according to an embodiment of the present invention. 12( b ) is a cross-sectional model explaining in detail the fine particles 1201 having a modified surface shape formed by being deposited on a substrate 1204 . The structure 1200 includes a substrate 1204 and fine particles 1201 having a modified surface shape formed by being deposited on the substrate 1204, and the fine particles 1201 having an active region 1203 including an amorphous phase. It combines with the adjacent particle 1201 with one junction area. Fine particles 1201 are deposited on the base material 1204 to constitute the covering portion 1205 . The structure 1200 is obtained when the density of the resulting structure is increased by using a large amount of kinetic energy from the ratio of the surface activation energy of the microparticles 1201 and the kinetic energy of the microparticles 1201, and by giving the raw material microparticles a particle size distribution. lose

12(a) and 12(b), the crystallites of the fine particles 1201 after deformation have a size of 1 nm or more and 300 nm or less. The volume of the fine particles 1201 after deformation has the volume of the starting raw material fine particles. An active region 1203 containing an amorphous phase is provided on the surface layer of the fine particles. When the obtained structure 1200 has a high compressive residual stress, the microparticles 1201 in the structure 1200 are refined, and the microparticles 1201 may be deformed. The base material 1204 forming the structure has a junction region with the active region 1203 including the amorphous phase of the surface layer of the fine particles 1201. Refined crystallites 1206 exist in the bonding region of the fine particles 1201 . The substrate 1204 is a porous material of, for example, brittle materials, metals, polymers, and materials. In the junction region including the amorphous phase, the fine particles 1201 and the fine particles 1201 form an interface by a combination of the raw material fine particles and the material of the substrate 1204, for example, a chemical bond such as a covalent bond or an ionic bond. It becomes the interface where the substrate 1204 is bonded. Bonding between the fine particles 1201 or between the fine particles 1201 and the base material 1204 is strengthened by the above-mentioned bonding, and the compressive stress applied to each bonding region enhances the mechanical strength of the bonding region.

The deformation of the particle 1201 is, for example, the long side (horizontal arrow in FIG. 12 (a)) and the short side (vertical arrow in FIG. 12 (a)) of one particle 1201 described in FIG. 12 (a). , when calculated by dividing the short side by the numerator and the long side by the denominator, the numerical value representing the deformation of the fine particle 1201 ranges from 0.1 to 0.99, and the volume of the deformed particle 1201 is the starting material before deformation as described above. has a volume of

13 is a cross-sectional model of a structure 1300 according to an embodiment of the present invention. The structure 1300 includes a substrate 1304 and fine particles 1301 whose surface shape is modified by being deposited on the substrate 1304. The fine particles 1301 form an active region 1303 including an amorphous phase. The branch is combined with the particle 1301 adjacent to it through the junction area. Fine particles 1301 have crystallites 1302. In addition, the structure 1300 has a junction region having an active region 1303 including an amorphous phase, and has a void 1307 that is not bonded to adjacent particles 1301 . The structure 1300 is obtained when, for example, a small amount of kinetic energy is used in the ratio between the surface activation energy of the fine particles 1301 and the kinetic energy of the fine particles. By lowering the ratio of kinetic energy among the energies required to form the structure 1300, the obtained structure has a low degree of impact fracture (crystal refinement) of the particles, and the dislocation inside the crystal grain is reduced, which is important for bonding between the fine particles. The compressive residual stress exerted on it is low. On the other hand, bonding between the particles is strengthened by the surface activation energy of the particles, so that a low-density structure is obtained. In this case, the fine particles in the structure 1300 are less refined than in the structure 1100, and the deformation of the particles is less than that in the structure 1100, and there is almost no deformation.

14(a) shows an enlarged view of a junction region between particles in a structure 1100 according to an embodiment of the present invention. 14( b ) shows an enlarged view of a junction region between particles of a structure 1200 according to an embodiment of the present invention. Among the structures shown in FIGS. 14(a) and 14(b), the bonding region between the particles is a region where the active regions of each of the extreme surface layers of the particles are joined, and are indicated by dotted lines in FIGS. 14(a) and 14(b). 14(a) and 14(b), bonds between atoms (shown as circles in the edges of FIGS. 14(a) and 14(b)) are cleaved or stretched by high-temperature electrons or ions, resulting in a disordered crystal structure. The active regions including each amorphous phase of were enlarged and displayed. In the junction region of the structure 1100, the microparticles 1101a and 1101b in the structure 1100 apply a compressive stress indicated by arrows in FIG. 14(a). Regarding the bonding area of the structure 1200, the microparticles 1201a and 1201b in the structure 1200 are subjected to compressive stress indicated by dotted arrows in FIG. grant to At this time, since the fine particles 1201a and 1201b in the structure 1200 are deformed by compressive stress, the fine particles 1201a and 1201b in the structure 1200 are larger than the fine particles 1101a and 1101b of the structure 1100. The fine particles 1201b are deformed. The compressive stress indicated by the arrow is greater in the structure 1100 than in the structure 1200. For example, the structure 1100 has a high compressive residual stress between the particles 1101 in the dense structure and the junction area between the particles 1101. Like the silver structure 1200, dislocations are introduced into the crystal grains by impact fracture (crystal refinement) of the fine particles 1201, and high compressive residual stress is applied to the bonding between the fine particles, so that the bonding between the fine particles 1101 is strengthened. has been

Reference is made to FIG. 15 here. 15 is a cross-sectional model of particulates having an active region including an amorphous phase formed by a method for manufacturing a structure according to the present invention. Fig. 15(a) shows single crystal fine particles 1010 as hexagonal single crystals, Fig. 15(b) shows them as hexagonal polycrystalline fine particles 1021 having crystallites 1022, and Fig. 15(c) shows crystallites 1032 Agglomerated powder 1030 in which hexagonal polycrystalline fine particles 1031 having are agglomerated is shown.

16 is a cross-sectional model explaining the details of the structure of a particle according to an embodiment of the present invention. 16(a) shows raw material particulates 1501 used to form a structure according to an embodiment of the present invention, and FIG. 16(b) shows a structure according to an embodiment of the present invention having a small deformation. The particulate 1101 is shown, and FIG. 16(c) shows the particulate 1201 having a large deformation constituting a structure according to an embodiment of the present invention. The raw material fine particles shown in FIG. 16 may be not only the polycrystal fine particles 1021 shown in FIG. 15 , but also single crystal fine particles 1010 or agglomerated powder 1030 obtained by aggregating raw material fine particles 1031 . The particulate is deformed by the applied compressive stress. The deformed particulate 1101 in FIG. 16(b) and the deformed particulate 1201 in FIG. 16(c) have the same volume as the raw material particulate 1501 in FIG. 16(a). As an index representing the deformation of fine particles, when calculated by dividing the short side and the long side of the fine particles with the short side as the numerator and the long side as the denominator, the numerical value is in the range of 0.1 to 0.99. An active region containing an amorphous phase generated by plasma or the like is provided on the surface layer of the fine particles in FIG. 16(b) or FIG. 16(c). When the deformation of the fine particles is large, at the same time, the crystallites in the fine particles are refined by impact crushing, and dislocations and distortions are formed, and the crystal lattice spacing is narrowed. When a strong compressive stress is applied, the surface layer of the fine particles in FIG. 16(c) becomes a surface layer 1211 having an amorphous phase generated by plasma or the like and a surface formed by impact grinding of the fine particles. For example, due to strong compressive stress, a part of the amorphous phase generated by plasma or the like in the surface layer of the fine particle in FIG. In the structure of the present invention, a structure in which fine particles having the characteristics of FIG. 16(b) or FIG. 16(c) or fine particles are mixed is formed.

When the starting material for forming the structure according to the above-described embodiment is the single crystal fine particle 1010, the active region 1013 can be formed on the surface of the structure by the method for manufacturing the structure according to the present invention. The single crystal fine particle ( 1010) does not progress as much as polycrystalline fine particles 1021, and single crystal fine particles 1010 are used as a starting material rather than polycrystalline fine particles 1021 as a starting material for reasons such as a small compressive stress applied to the joint region. The mechanical strength of the structure to be low. Further, when the starting material for forming the structure according to the embodiment of the present invention is the agglomerated powder 1030 in which the polycrystalline fine particles 1031 are aggregated, the range of the active region 1033 activated by plasma or the like is the agglomerated powder 1030 ), or a part of the impact grinding of the fine particles is used for crushing the agglomerated powder 1030, etc. The mechanical strength of the structure is low. Although affected by the physical properties of the starting materials, etc., the mechanical strength of the structure increases in the order that the raw material particles used are agglomerated powder < single crystal fine particles < polycrystalline fine particles. When the microparticles are agglomerated during the formation of the structure, an active region 1023 is formed on the surface of the polycrystalline microparticles 1021 by adding a method for canceling the aggregation state of the microparticles using a crusher or the like to the microparticles previously aerosolized. This formation further increases the mechanical strength and uniformity of the structure obtained.

[Method for manufacturing structure]

The structure according to the present invention described above can be manufactured using, for example, the apparatus 2000 for manufacturing a structure shown in FIG. 17 . In addition, one embodiment of the structure manufacturing method according to the present invention will be described along with the steps shown in FIG. 18 . The apparatus 2000 for manufacturing a structure includes, for example, an aerosol generator 2103, a structure manufacturing unit 2107, and a power source 2108 for generating plasma. Furthermore, it is preferable that the apparatus 2000 for manufacturing a structure includes a grinder 2105 for releasing agglomerated particles and secondary particles formed by granulation in the raw material fine particles into a state of primary particles. An aerosol generator 2103 is connected to a cylinder 2101 for conveying and plasma generating gas via a gas conveying pipe 2102. The aerosol generator 2103 is connected to the mill 2105 via an aerosol delivery tube 2104. The grinder 2105 is connected to the structure manufacturing unit 2107 via an aerosol delivery tube 2106.

A plasma generating device 2109 is disposed in the structure manufacturing unit 2107, and an aerosol transport pipe 2106 is connected to one end of the plasma generating device 2109. A nozzle 2110 is disposed at the other end of the plasma generating device 2109. As the plasma generator 2109, for example, an induction coil can be used. Further, in the structure manufacturing section 2107, a stage 2112 is disposed at a position facing the nozzle 2110, and a substrate 2111 is disposed on the stage 2112 so as to face the nozzle 2110. The structure production unit 2107 is connected to a vacuum pump 2113 for depressurizing and degassing the inside of the structure production unit 2107 . The grinder 2105 is preferably disposed in front of the plasma generator 2109.

The raw material fine particles 2301 are supplied with an inert gas such as argon or helium from an aerosol generator 2103, for example, from a transport and plasma generating gas cylinder 2101 (S101), and mixed and stirred with the supplied gas type. It is aerosolized (S103). Subsequently, in the temperature range below the melting point of the fine particles, the surface of the fine particles is electronically excited by using the aerosol transport path in the plasma generator 2109 or the non-thermal equilibrium plasma generated in the nozzle 2110, etc., continuously in the active region ( 2130) is generated (S105). In the aerosol conveyance path in the plasma generating device 2109, the energy is highest in the vicinity immediately below the induction coil, for example, and the particles are conveyed inside the plasma, which becomes a high energy space, for 10 ^-2 seconds, preferably. An active region is created on the surface layer of the microparticles between 10 ^-3 seconds and 10 ^-5 seconds. The high-energy space in the aerosol transport path of the plasma generating device 2109, which provides an active region to the surface layer of the fine particles, is preferably at a temperature equal to or lower than the melting point of the raw material fine particles. The aerosol containing the fine particles 2302 to which the active area 2130 is applied is ejected onto the substrate 2111 (S107). When the fine particles 2302 reach the substrate 2111, the fine particles 2302 and each other and the fine particles 2302 and the substrate 2111 are activated by the surface activation energy of the fine particles 2302 and the kinetic energy of the fine particles 2302. A bonding area bonded through the area is formed. The plasma used for generating the active region of the surface layer of the microparticles has a plasma flame reaching the substrate, but preferably does not cause thermal damage to the substrate. The active region of the surface layer of the fine particles generated by the plasma is maintained until the fine particles reach the substrate by flying in the plasma flame, and through the active region generated by the plasma and the active region generated by collision and crushing of the fine particles, The fine particles are bonded to each other and the fine particles and the base material are bonded. Accordingly, the fine particles 2302 are deposited on the surface of the substrate 2111 to form the coating layer 2305, and the structure 2307 can be manufactured.

According to one embodiment of the present invention, bonding between fine particles by a bonding region through an active region including an amorphous phase applied to the surface of the fine particles or the surface of a substrate by plasma or the like, and collision crushing (crystal refinement) of the fine particles into crystal grains By introducing dislocations and imparting a high compressive stress to the bonding between the microparticles to enhance the bonding between the microparticles, the mechanical strength of the structure is improved. According to one embodiment of the present invention, an active region is formed on the surface of the primary particle by the impact fracture effect of the primary particle and the thermal effect of the plasma. In addition, according to one embodiment of the present invention, by applying the thermal effect of plasma to the impact crushing effect of the primary particles, the active area on the surface of the primary particles is increased, and the efficiency of using the raw material fine particles used to form the structure is increased.

In the conventional thermal spraying method, when forming a dense structure, it is necessary to melt the entire particle and promote material flow by heat, so it is not easy to make the thickness of the amorphous phase formed in the junction region between the particles ultra-thin. In contrast, according to the embodiment of the present invention, it is possible to precisely create a junction region between fine particles.

19(a) is a cross-sectional model of the particle 1040 in which the raw material particle 1041 by the conventional aerosol deposition method is collided and deformed, and FIG. 19(b) is a raw material by the manufacturing method according to an embodiment of the present invention. The particle 1041 is a cross-sectional model of the particle 1050 in which the particle 1041 is crushed and deformed by collision. In addition, FIG. 20 (a) is a cross-sectional model of the bonding between particles/substrate by a conventional aerosol deposition method, and FIG. 20 (b) is a cross-sectional model of bonding between particles and particle/substrate by a manufacturing method according to an embodiment of the present invention. It is a cross-sectional model of liver coupling. According to one embodiment of the present invention, in the conventional aerosol deposition method, as shown in FIGS. 19(a) and 20(a), a crushed surface formed by impact grinding is used as an active region (new surface) 1044. Thus, bonds between particles and between particles/substrate are formed. For this reason, the inactive region 1045 corresponding to the particle surface before crushing is in an inactive state even after particle crushing, and therefore, the surfaces of the particles refined by pulverization are not all activated. Therefore, there is an inactive region 1045 on a part of the surface of particles refined by crushing, and when the surfaces of such inactive regions are in contact with each other or one contact surface is inactive, a strong bond cannot be formed, and the refined particles or The micronized particles and the substrate are repelled and do not contribute to the formation of the structure. Therefore, the utilization efficiency of the raw material fine particles forming the structure is low, which is a major problem in practical use. According to one embodiment of the present invention, as shown in FIGS. 19(b) and 20(b), the surface of the inactive raw material particle before crushing is exposed to plasma 1080 to activate in advance, and the surface is activated in this way. When the raw material particles are refined by collision crushing, the surfaces of the refined particles all become active regions 1053 and 1054, and densification proceeds by the flow of the fine particles, and at the same time, fine particles whose surfaces are all activated by being refined are Just by contacting the fine particles with the substrate, a strong bond is easily formed, greatly improving the efficiency of using the raw material powder involved in the formation of the structure, and it is possible to form a dense film to a porous film with good controllability. Accordingly, as shown in FIG. 20(b), an active region 1053 contributing to bonding of the surface of the fine particle formed by impact grinding and an active region 1054 including the amorphous phase of the surface layer of the fine particle formed by exposure to plasma By bonding through, it is possible to form a structure having practical use efficiency and formation speed of raw material powder or practical strength or density.

In the conventional aerosol deposition method, the shape of the substrate bonded to the structure is preferably a flat shape, and the structure is formed on the substrate having a complicated shape by a method in the manufacturing process, but the substrate is sharp or has a small radius of curvature. When there is an edge portion, the impact compressive force is not sufficiently applied to the colliding particles in the vertical direction, and since the formation of the active region by particle crushing does not proceed, the colliding particles repel the substrate, so that a film or structure cannot be formed. . Rather, shear force acts between the particles and the substrate, the particles are not pulverized, the substrate is etched, or a repeated compressive force is applied to the surface of the deposited film or structure, so internal stress increases, and the bonding force with the substrate is weak, There has been a problem such as occurrence of peeling from the base material of the film or structure. According to one embodiment of the present invention, the internal stress of the structure is reduced by bonding the fine particles or the fine particles and the substrate through an active region including an amorphous phase generated by plasma or the like as well as an active region generated by impact pulverization of fine particles. Relaxation and fine adjustment are possible, and by increasing the area of the active region contributing to the bonding between the surface of the fine particles and the surface of the substrate, the structure can be directly formed on the substrate without the need for pretreatment or the like. For example, a structure can be formed on the edge part of a base material, or in the shape of a circle or sphere.

Further, even on the surface of a substrate having a concavo-convex shape on the surface, such as a porous substrate, the fine particles or the fine particles and the substrate are bonded to each other or to the substrate through an active region containing an amorphous phase generated by plasma or the like and an active region generated by impact grinding of the fine particles, The area of the active region contributing to bonding between the surface of the fine particle and the surface of the substrate can be increased, and a structure can be directly formed without the need for pretreatment or the like. In addition, in the conventional aerosol deposition method, it is not easy to impart a high compressive residual stress to the structure by impacting and crushing the microparticles under the influence of the shape of the substrate, such as irregularities. Although it was not easy to do this, according to an embodiment of the present invention, bonding between fine particles by the bonding region through an active region including an amorphous phase applied to the surface of the fine particles or the substrate surface, and impact crushing of the fine particles (crystal refinement) By introducing dislocations into the crystal grains and applying high compressive stress to the bonding between the microparticles, it is possible to strengthen the bonding between the microparticles, thereby directly forming a structure having compressive residual stress. Further, in one embodiment of the present invention, in the bonding region between the fine particles and the substrate, the temperature of the surface of the raw material fine particles exposed to the plasma is brought close to the thermoplastic temperature of the resin substrate or the like, so that the soft thermoplastic resin substrate requires pretreatment or the like structure can be formed directly without

In addition, according to the present invention, by giving a thickness to the joint area, which is the above-described structural feature, by giving the raw material fine particles a particle size distribution, and by giving a compressive residual stress in the structure, a continuously inclined structure structure can be formed. According to one embodiment of the present invention, for example, a structure having a high density from the surface of a substrate having a low density in the above-described porous substrate provides an active area to the surface layer of the microparticles, and the value of the short/long sides of the deformable microparticles in the structure is . Further, according to an embodiment of the present invention, surface chemical reactions such as gas exchange reactions, adsorption reactions, and reforming reactions are enhanced by using an active region on the surface of the microparticles that does not contribute to bonding between the surfaces of the microparticles or between the surfaces of the microparticles and the surface of the substrate. A structure that maintains a high density of reaction characteristic fields can be formed.

In addition, according to the present invention, bulk materials and thermal sprayed coatings are formed by providing a thickness in the joint area, which is the above-mentioned structural feature, and having a particle size distribution in the raw material fine particles, and having a compressive residual stress in the structure. It is possible to form a structure having a thinner thickness and higher insulating properties and thermal properties.

Example

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited to these examples.

The basic configuration of the apparatus 10 for forming an ultra-fine particle structure for a plasma source used in this embodiment is the same configuration as shown in FIG. 3 . Therefore, redundant description is omitted. A coil for generating inductively coupled high-frequency plasma is wound 3 to 4 times. The inner diameter of the nozzle of the part generating the high-frequency plasma is 8 to 27 mm. The shape of the opening of the nozzle used to inject the ceramic fine particles onto the substrate is a square of 1mm x 10mm or a circle of 5mm to 27mm. As the type of plasma gas, argon, helium, nitrogen, dry air or a mixed gas of argon and oxygen was used. The gas flow rate was 0.5 to 40 SLM (standard state L/min). The power was in the range of 0.5 to 6 kW. The pressure in the deposition chamber was in the range of 20 Pa to 2 kPa.

In addition, the plasma flow and the flow of plasma particles were simulated by commercially available high-frequency plasma analysis software. In addition, a reference temperature was measured using a thermocouple. The raw material fine particles are α-alumina (AL160-SG manufactured by Showa Denko, AA-02~5 manufactured by Sumitomo Chemical, Tymecron, abrasive powder manufactured by Fuji Corporation), yttria stabilized zirconia (8YSZ manufactured by Jeil Rare Element Chemicals, Toso ( 8YSZ) manufactured by Tosoh Corporation) was used. As the substrate, stainless steel, resin, aluminum, and glass substrates were used.

(Example 1)

In the above production method, the film formation results are shown when α-alumina particles (AL160-SG manufactured by Showa Denko) were used as raw material particles and a stainless steel substrate was used as the base material. The distance between the nozzle and the substrate was 20 mm, the inner diameter of the nozzle was 10 mm, and argon was used as the plasma gas. The indicated value of the thermocouple placed at the film formation position was about 200°C. 4(a) to 4(d) are scanning transmission electron microscope images and electron energy loss spectroscopy mapping diagrams of cross-sections of the structures obtained at this time. That is, FIG. 4(a) is an annular dark field image obtained by a scanning transmission electron microscope. 4(b) is the mapping result of α-alumina by electron energy loss spectroscopy, FIG. 4(c) is the mapping result of γ-alumina by electron energy loss spectroscopy, and FIG. 4(d) is the result of mapping by electron energy loss spectroscopy. This is the mapping result of amorphous alumina. The sample was thinned to a thickness of 80 nm, observed with a scanning transmission electron microscope, and also acquired an electron energy loss spectroscopy spectrum from the cross section. Identification of α-alumina, γ-alumina, and amorphous alumina was determined by performing fitting by comparing with respective reference data in the range of 75 eV to 90 eV in the electron energy loss spectroscopy spectrum. From this result, it can be seen that a three-dimensional network 202 of an amorphous alumina phase, which is an activation stage and has a thickness of about 20 nm, is formed between the brittle material particles 201 (FIG. 4(d)). The spacing between the particles is approximately 50 nm or less. As shown in the schematic diagram of FIG. 2, amorphous material exists between the alumina particles, which is a brittle material, and has a cross-linked structure connecting the brittle material particles to each other. In addition, it was found to be a structure in which α-alumina, which is the brittle material particle 201, is present in the three-dimensional network 202 (FIG. 4(a), FIG. 4(d)). At this time, as shown in FIG. 4(c), γ-alumina was not included.

5 shows X-ray diffraction results when the structure was formed on a glass substrate under similar conditions (structure (Ar)). For comparison, the X-ray diffraction results of α-alumina particles (AL160-SG manufactured by Showa Denko) powder and the X-ray diffraction results of the case where helium gas was used as the plasma gas (structure (He)) are also shown. The crystal structure of the powder or structure was analyzed by X-ray diffraction (XRD, Rigaku RINT-2550V, CuKa 40kV 200mA). In the case of using argon gas as the plasma gas (structure (Ar)) and the case of using helium gas as the plasma gas (structure (He)), peaks similar to α-alumina powder were observed, and the results of the electron energy loss spectroscopy spectrum and Similarly, only α-alumina was observed, and γ-alumina was not observed. At this time, when argon gas was used as the plasma gas, the crystallite size of the brittle material particles was calculated using the Scherrer equation and was about 50 nm. The crystallite size of brittle material particles when helium gas is used as the plasma gas is about 20 nm when calculated using the Scherrer equation, and the crystallite size tends to be smaller than that of the raw material powder.

The film hardness was measured using a dynamic hardness meter equipped with a Vickers indenter (SHIMADZU DUH-211), and the Vickers hardness at this time was Hv300. The hardness of this structure corresponds to a value of about 0.2 to the Vickers hardness of brittle material particles.

(Comparative Example 1)

Fig. 6 shows a scanning transmission electron microscope image of a cross section of α-alumina particles (AL160-SG3 manufactured by Showa Denko), which is a raw material particle. The X-ray diffraction result of the raw material particles was α-alumina as shown in FIG. 5 . A parallel lattice pattern can be observed up to the outermost surface of the alumina particles 301 showing crystallinity (303a) and the outermost surface of the particle (303b), crystals up to the surface, and amorphous alumina is present in the initial raw material powder. You can see that it doesn't. Even when these raw material particles were laminated as they were, they did not bond with each other and only formed a green compact.

(Comparative Example 2)

7 shows a scanning transmission electron microscope image of a cross-section of a structure obtained when α-alumina particles (manufactured by Fujimi Incorporated) were sprayed by conventional plasma spraying. Since the particle is melted to the inside of the particle by the plasma and is flat at the time of collision, the brittle material particle to be constituted assumes a flat anisotropic shape in the collision direction, and an isotropic structure cannot be formed. In addition, it can be seen that crystal growth occurs in each brittle material particle in parallel with the direction of heat extraction, because the material is rapidly cooled and solidified by heat extraction to the substrate. As a result of electron energy loss spectroscopy and X-ray diffraction, the brittle material particles were γ-alumina and had a crystal structure different from that of the initial brittle material particles, and the initial crystal structure could not be maintained.

(Example 2)

Yttria-stabilized zirconia particles (made by Jeil Rare Element Chemicals, 8 weight percent, average particle diameter: 3 μm) were used as the raw material particles, and a stainless steel substrate was used as the substrate. Plasma was generated with a power of 6 kW by flowing 10 SLM of argon gas. At this time, the pressure in the deposition chamber was about 400 Pa. The distance between the nozzle and the substrate was 200 mm and the inner diameter of the nozzle was 27 mm. 8 is a scanning transmission electron microscope image of a cross-section of the structure obtained at this time. It can be seen that it has the same structure as Example 1. The Vickers hardness of the structure of Example 2 was 620 Hv because the powder was not simply a compacted green compact and the particles were equally bonded in a three-dimensional network structure. This value corresponds to a relative hardness of the order of 0.5 to the Vickers hardness of brittle material particles.

(Comparative Example 3)

Under the conditions of Example 2, but under a pressure of 2 kPa, a structure was formed, and the obtained structure was a green compact.

(Example 3)

It was carried out under the conditions of Example 1, but by changing the gas type to helium. From the results of X-ray diffraction (FIG. 5) of the obtained structure, it was α-alumina and the Vickers hardness was 1230 Hv. This value corresponds to a value of about 0.7 to 0.8 for the Vickers hardness of brittle material particles.

(Example 4)

9 shows a transmission electron microscope image of the structure obtained under the same conditions. There is a substrate surface at the bottom of the drawing, and by combining the main brittle material particles of the structure of Example 4 with a room temperature impact hardening phenomenon using energy during collision, the shape of the brittle material particles flat in the direction perpendicular to the substrate while maintaining the basic structure can be obtained. It can be formed, and it is possible to achieve densification.

(Example 5)

In the above production method, the result of film formation when α-alumina particles (AL160-SG3 manufactured by Showa Denko) was used as the raw material particle and a porous ceramic substrate having an average pore diameter of 20 μm was used as the substrate was shown. Plasma was generated with a power of 1 kW by flowing 10 SLM of argon gas. 10 shows a cross-sectional scanning electron microscope image of a laminate in which a brittle material structure 1001 is deposited on a porous substrate 1002. It can be seen that the structure of Example 5 makes it possible to manufacture the encapsulation structure of the porous substrate.

(Example 6)

As raw material particles, yttria-stabilized zirconia particles (made by Jeil Rare Element Chemical Industry Co., Ltd., 8 weight percent, average particle diameter: 5 μm) were used, and a stainless steel substrate was used as the substrate. Plasma was generated with a power of 6 kW by flowing 10 SLM of argon gas. At this time, the pressure in the deposition chamber was about 300 Pa. The distance between the nozzle and the substrate was 200 mm and the inner diameter of the nozzle was 27 mm. The Vickers hardness of the structure of Example 6 was about 940 Hv or more and 1400 Hv or less. This value corresponds to a relative hardness of about 0.7 or more and 1.1 or less to the Vickers hardness of brittle material particles.

(Example 7)

Film formation results when α-alumina particles (AL160-SG manufactured by Showa Denko) were used as raw material particles are shown. The distance between the nozzle and the substrate was 20 mm, the inner diameter of the nozzle was 10 mm, and argon was used as the plasma gas. The insulation properties of the structure were measured by depositing a gold electrode (1 mm ² ) on the structure by a sputtering method using a device (Model 6252 Rev. C) manufactured by Dongyang Technica, and measured by a two-terminal method. The volume resistivity was 10 ¹² Ω·cm or more and 10 ¹⁵ Ω·cm or less, and the dielectric strength was 50 kV/mm or more and 200 kV/mm or less, and exhibited high electrical sealing characteristics.

(Example 8)

The conditions were the same as in Example 7, and helium was used as the plasma gas. The insulating properties of the structure were measured by a two-terminal method after depositing a gold electrode (1 mm ² ) on the structure by a sputtering method using a device manufactured by Dongyang Technica (Model 6252 Rev. C). The volume resistivity was 10 ¹² Ω·cm or more and 10 ¹⁵ Ω·cm or less, and the dielectric strength was 100 kV/mm or more and 300 kV/mm or less, and exhibited particularly high electrical sealing characteristics.

In addition, the dielectric strength test can be performed with direct current or alternating current, and in this embodiment, even when argon gas is used, the laminated structure can achieve an dielectric strength of 20 kV/mm or more even when measuring both direct current and alternating current. For example, when argon gas was used, the gas flow rate was 20 L/min, and the plasma power was 0.5 kW to 2 kW, a withstand voltage of 2 kV or more was exhibited even with a thickness of about 20 μm ( FIG. 36 ). With the impact fracture of the fine particles (crystal refinement), a structure with a high compressive residual stress is formed. As a result, a structure having insulating properties higher than that of the bulk alumina sintered body, which generally exhibits an electric field strength of 12 to 15 kV/mm, is formed.

In the structure according to one embodiment of the present invention, a high withstand voltage of 1 kV or more, preferably 2 kV or more, can be secured even when the insulating layer is composed of a thin coating layer having a thickness of 50 μm or less. Therefore, if the structure according to one embodiment of the present invention is used, it is possible to form a high-voltage circuit board having lower thermal resistance (excellent heat dissipation) than bulk materials or thermal sprayed coatings, and as a heat dissipation substrate for automotive power modules or high-power LEDs. desirable.

FIG. 21 is a scanning transmission electron microscope image and electron energy loss spectroscopy mapping diagram of a particle in a structure showing characteristics of a structure according to an embodiment of the present invention when α-Al ₂ O ₃ is used as a raw material particle. FIG. 21(a) shows a scanning transmission electron microscope image of particulates, and FIG. 21(b) shows a mapping diagram of electron energy loss spectroscopy. In addition, for comparison with the particles in the structure, a surface observation image using the above-described raw material particles is shown in FIG. 22 . Raw material fine particles, Al ₂ O ₃ , are generally brittle materials with a high melting point of 2000° C. or higher, and the α phase is the most stable. In addition, when Al ₂ O ₃ melted by a conventional thermal spraying method is quenched and solidified, Al ₂ O ₃ having a γ phase is included in the structure. The fine particles 1021a and 1021b in the structure shown in FIG. 21 have the α phase as the main phase similar to the starting material α-Al ₂ O ₃ shown in FIG. An active region 1023 to be observed has been created. In the microparticle 1021a of FIGS. 21(a) and 21(b), since the microparticle surface layer has an amorphous phase, the active region 1023 containing the amorphous phase that is not bonded to other microparticles and does not contribute to bonding of the microparticle surface layer ) is observed. The periphery of the space existing in the structure, such as the space indicated by the solid black line in FIG. 21(b), is surrounded by the active region 1023 including the amorphous phase formed on the surface layer of the microparticles. . As shown in the dotted line in FIG. 21(b), for example, in a dense structure, fine particles are densely adjacent to each other, and the entire circumference thereof is surrounded by an active region 1023 containing an amorphous phase of the fine particles. In the microparticles 1021b of FIGS. 21(a) and 21(b), since the microparticle surface layer has an active region 1023 containing an amorphous phase, an amorphous phase surrounding the microparticles is observed. However, in the present embodiment, since only the α phase was observed without including the γ phase inside the microparticles, the microparticles were not affected by heat. Comparing FIG. 21 and FIG. 22, the fine particles 1021 create an active region 1023 during the process of forming a structure, and the fine particles are bonded together through the active region, such as the bonding region between the fine particles in FIG. can be said to be from When the active region 1023 is created on the surface layer of the fine particles 1021 by plasma or the like and the fine particles are bonded together through the active region 1023, for example, three adsorbed water (physical adsorbed water) is formed on the Al ₂ O ₃ surface. , chemically adsorbed water, surface hydroxyl groups), and by removing surface hydroxyl groups that escape at 1000° C. or higher, an electronically excited active region 1023 including an amorphous phase observed in FIG. 21 is obtained. Further, by activating the microparticles with a heat source such as plasma at 2000° C. or less, which is equal to or lower than the melting point of Al ₂ O ₃ , or within a range of contact time that does not melt alumina, the structure of this embodiment is obtained.

α-Al ₂ O ₃ (FIG. 23(a)) used as a starting material in FIG. 23, a cross-sectional transmission electron microscope image of a structure according to the present invention formed using fine particles (FIG. 23(b)) and a starting material as a comparison A cross-sectional transmission electron microscope image (FIG. 23(c)) of the structure formed by the aerosol deposition method using was shown. In this embodiment, the microparticles have an active region containing an amorphous phase as described above, and there are cases in which the crystallite size of the starting material is maintained, and micronization of the microparticles as in the aerosol deposition method other than the above case also occurs. When forming the structure of the present embodiment, when a large amount of kinetic energy is used in the ratio of the surface activation energy of the fine particles to the kinetic energy of the fine particles, dislocations are introduced into the crystal grains by collision fracture (crystal refinement) of the fine particles, and between the fine particles A high-density structure is obtained in which the bonding between the microparticles is strengthened by applying a high compressive residual stress to the bonding. In the portion enclosed by the broken line in FIG. 23(b), dislocations are introduced into the crystal grains by collision fracture (crystal refinement) of the particles, high compressive residual stress is applied to the bonding between the particles, and the bonding between the microparticles is strengthened. Distortion inside the microparticles is observed indicating that The crystallite diameter of the microparticles included in the structure shown in FIG. 23(b) (for example, the portion of FIG. 23(b) surrounded by a broken line), even if the crystallite diameter is refined due to collision pressure on the microparticles, the crystallite size due to heat Coarseness of the diameter cannot occur. In addition, since impact crushing (crystal refinement) of fine particles by impact pressure is mitigated by the active region containing an amorphous phase applied to the polar surface layer of the microparticles, impact crushing (crystal refinement) of fine particles like an aerosol deposition method using only impact pressure for comparison can be said not to proceed. Therefore, the crystallite size of the microparticles in the structure according to this embodiment is not coarsened compared to that of the starting material microparticles, and has a crystallite size of 1 nm to 300 nm.

(Example 9)

In order to form a structure according to the present invention, an embodiment in which a structure is formed in a reduced pressure environment using α-Al ₂ O ₃ as fine particles and SUS304 as a substrate will be described. Helium gas was used as a type of gas that aerosolizes and supplies and transports fine particles, generates non-equilibrium plasma that activates the surface layer of fine particles at a temperature below the melting point, and accelerates and ejects fine particles that act as an impact force to the substrate. A range of 0.5 to 2 kW of high-frequency input power for generating non-equilibrium plasma was used. The hardness of the structure was measured using a dynamic hardness tester equipped with a Vickers indenter (SHIMADZU DUH-211).

24(a) shows a cross-sectional scanning electron microscope (SEM) image of the structure 1600 obtained. In the structure 1600, it was observed that an overlayer 1605 was formed on the substrate 1604. 25 shows the X-ray diffraction pattern of the obtained structure. In the X-ray diffraction pattern of the structure 1600, no peak due to the γ phase was observed. The raw material fine particles (α-Al ₂ O ₃ ) did not melt because they were not heated above a temperature of about 2000° C., which is the melting point of the particles, and the fine particles in the obtained structure 1600 did not undergo crystal phase transformation to the γ phase. That is, a structure maintaining the α-phase crystal structure of the raw material fine particles was formed, and a dense coating layer 1605 made of α-Al ₂ O ₃ with a thickness of about 50 μm was formed on SUS304 as the substrate 1604. The crystallite diameter in the obtained structure 1600 was about 30 nm when estimated using the Scherer equation for calculating the crystallite diameter using the peak width of the X-ray diffraction pattern. The Vickers hardness of the structure obtained was Hv700 to Hv1300.

28 shows the utilization efficiency ratio of the raw material fine particles of Example 9. The utilization efficiency of the raw material fine particles was calculated with the weight of the used raw material fine particles as the denominator and the weight increased by forming the structure of the substrate as the numerator. As shown in FIG. 28 , the use efficiency of the particles forming the structure 1600 increased tenfold by activating the surface layer of the particles at a temperature below the melting point using nonthermal equilibrium plasma.

(Example 10)

In order to form the structure according to the present invention, an example in which α-Al ₂ O ₃ is used for the fine particles and SUS304 is used for the substrate to form the structure in a reduced pressure environment will be described. Argon gas was used as a type of gas that aerosolizes and supplies and conveys the fine particles, generates non-equilibrium plasma that activates the surface layer of the fine particles at a temperature below the melting point, and accelerates and ejects the fine particles that act as an impact force to the substrate. A range of 0.5 to 2 kW of high-frequency input power for generating non-equilibrium plasma was used. The hardness of the structure was measured using a dynamic hardness tester equipped with a Vickers indenter (SHIMADZU DUH-211).

24(b) shows a cross-sectional SEM image of the structure 1700 obtained. In the structure 1700, it was observed that an overlayer 1705 was formed on the substrate 1704. 26 shows the X-ray diffraction pattern of the obtained structure. In the X-ray diffraction pattern of the structure 1700, no γ-phase peak was observed. Since the raw material fine particles (α-Al ₂ O ₃ ) were not heated to a temperature higher than about 2000° C., which is the melting point of the fine particles, they did not melt and were not quenched. Therefore, the fine particles in the obtained structure 1700 undergo crystalline phase transformation to the γ phase. did not cause That is, a structure maintaining the α-phase crystal structure of the raw material fine particles was formed, and a coating layer 1705 made of α-Al ₂ O ₃ with a thickness of about 150 μm was formed on SUS304 as the substrate 1704. The crystallite diameter in the obtained structure 1700 was about 70 nm estimated using the Scherrer equation for calculating the crystallite diameter using the peak width of the X-ray diffraction pattern. Vickers hardness of the structure obtained was Hv300 to Hv900. 29 shows the utilization efficiency ratio of the raw material fine particles of Example 10. The utilization efficiency of the raw material fine particles was calculated with the weight of the raw material fine particles used as the denominator and the weight increased by forming the substrate structure as the numerator. As shown in FIG. 29 , the use efficiency of the particles forming the structure 1700 is increased 50 times by activating the surface layer of the particles at a temperature below the melting point using non-thermal plasma.

27 shows X-ray diffraction patterns of the structures obtained in Examples 9 and 10. All of the α-Al ₂ O ₃ peaks in the X-ray diffraction pattern of the structure 1600 of Example 9 are shifted to the wide-angle side. Meanwhile, in Example 10, the aforementioned α-Al ₂ O ₃ peak change was not observed. In the above-mentioned X-ray diffraction pattern, in Example 9, it is considered that the α-Al ₂ O ₃ peak shifted to a wide angle because compressive stress was introduced into the structure and the crystal lattice spacing in the microparticles narrowed, and the compressive stress in the structure confirmed an increase in On the other hand, in Example 10, a large change in the α-Al ₂ O ₃ peak at a wide angle as in Example 9 was not observed, and it was confirmed that the internal stress was smaller than in Example 9.

(Example 11)

According to the present invention, dislocations are introduced into the inside of the crystal grains by bonding between the fine particles by the bonding region through an active region including an amorphous phase applied to the surface of the fine particles or the surface of the substrate, and impact crushing of the fine particles (crystal refinement), thereby introducing dislocations between the fine particles. A structure obtained when a high compressive residual stress is applied to the bonding to enhance bonding between fine particles and an example in which the Vickers hardness and electrical properties of the structure are measured will be described. In general, since the higher the density of the structure, the higher the Vickers hardness and the higher the electrical properties, so it was also used in the Examples as an index indicating the compactness of the density. The Vickers hardness of a structure formed in a reduced pressure environment using α-Al ₂ O ₃ for fine particles and SUS304 for a base material will be described. The hardness of the structure was measured using a dynamic hardness tester equipped with a Vickers indenter (SHIMADZU DUH-211). The electrical properties of the structure were measured by the two-terminal method by depositing gold electrodes (1 mm ² ) on the structure by sputtering using a device (Model 6252 Rev. C) from Dongyang Technica. Helium gas and argon gas are used as gases for aerosolizing and supplying and transporting fine particles, generating non-equilibrium plasma that activates the surface layer of fine particles at a temperature below the melting point, and accelerating and ejecting fine particles that act as an impact force on the substrate. did Table 1 summarizes the Vickers hardness of the obtained structure and the gas flow rate, plasma power, and temperature in the particulate structure manufacturing section 2107 measured using a thermocouple when the structure was obtained. As the electrical properties of the obtained structure, the volume resistance and dielectric strength are summarized in Table 2.

gas type input power [kW] Gas flow [L/min] Temperature [℃] Vickers hardness He 2 10 300 700 1.5 10 200 900 One 10 150 1100 5 125 800 0.5 10 125 1300 5 100 700 Ar 2 10 1300 200 1.5 10 1000 250 One 20 300 900 15 500 700 10 700 500 5 500 300 0.5 10 300 750

type Volume resistance value Ω cm Dielectric strength kV/mm He 10 ¹² ~10 ¹⁵ 100 to 300 Ar 10 ¹² ~10 ¹⁵ 50 to 200

As shown in Table 1, the temperature of the helium gas and the argon gas is lower than that of the argon gas. In addition, the flight speed when the above-mentioned particles are accelerated and ejected is faster than the helium gas using the argon gas. Here, the higher the temperature, the higher the surface activation energy of the active region imparted to the extreme surface layer of the fine particles, and the bonding between the fine particles or between the fine particles and the substrate is promoted. In addition, as the flight speed of the fine particles increases, the kinetic energy of the above-described fine particles increases, and the compressive stress applied to the miniaturization or bonding area of the particles increases. As shown in Table 1, a dense structure was formed by the sum of surface activation energy and kinetic energy. For example, in Table 1, when the gas type is helium gas, the gas flow rate is 10 L/min, and the plasma power is 0.5 kW, a structure with high compressive residual stress is formed due to collision fracture (crystal refinement) of fine particles. is formed As a result, a structure with a high Vickers hardness is formed. For example, in Table 1, when the gas type is argon gas, the gas flow rate is 10 L/min, and the plasma power is 2 kW, the bonding between the particles is strengthened by the surface activation energy of the particles, resulting in a compressive residual stress. structure is formed. As a result, a structure having a low Vickers hardness was formed. In addition, when helium gas was used, the dielectric strength of the structure was 100 kV/mm or more and 300 kV/mm or less. In the case of using argon gas, the dielectric strength of the structure was 50 kV/mm or more and 200 kV/mm or less. As an example, a structure in which coating layers are stacked may be formed. The dielectric withstand voltage test can be performed with either direct current or alternating current. In this embodiment, even when argon gas is used, the laminated structure can achieve an dielectric strength of 20 kV/mm or more in both direct current and alternating measurements. For example, when argon gas was used, the gas flow rate was 20 L/min, and the plasma power was 0.5 kW to 2 kW, a withstand voltage of 2 kV or more was exhibited even with a thickness of about 20 μm ( FIG. 36 ). With the impact fracture of the fine particles (crystal refinement), a structure with a high compressive residual stress is formed. As a result, a structure having insulating properties higher than that of the bulk alumina sintered body, which generally exhibits an electric field strength of 12 to 15 kV/mm, is formed.

The structure according to the present invention can secure a high withstand voltage of 1 kV or more, preferably 2 kV or more, even when the insulating layer is a thin coating layer having a thickness of 50 μm or less. Therefore, when the structure according to the present invention is used, it is possible to form a high-voltage circuit board having lower thermal resistance (good heat dissipation) than bulk materials or thermal sprayed coatings, and is suitable as a heat dissipation substrate for automobile power modules or high-power LEDs.

(Example 12)

An example in which the structure of the present invention is formed using α-Al ₂ O ₃ as fine particles and a ceramic porous substrate having an average pore diameter of 20 μm as a substrate will be described. Argon gas was used as a type of gas that aerosolizes and supplies and conveys fine particles, generates non-equilibrium plasma that activates the surface layer of fine particles at a temperature below the melting point, and accelerates and ejects particles that act as an impact force on the substrate. The high-frequency input power for generating non-equilibrium plasma was set to 1 kW.

30 shows a cross-sectional image of a structure 1800 using the porous ceramic of Example 12 as a substrate 1804 by means of a scanning transmission electron microscope. Fig. 30(b) is an enlarged view of Fig. 30(a). As shown in FIG. 30, even on a substrate having a conventionally difficult surface shape, according to the present invention, through an active region including an amorphous phase applied to the surface of the fine particles or the interface between the substrate and between the fine particles by the bonding region and between the fine particles and the substrate Dislocations are introduced into the crystal grains by bonding and impact fracture (crystal refinement) of the microparticles, and a high compressive residual stress is applied to the bonding between the microparticles to strengthen the bonding between the microparticles, thereby forming a dense coating layer 1805. A structure 1800 was formed. As shown in the circled portion of FIG. 30 (b), with respect to pores existing on the surface of the substrate 1804, fine particles as a starting material contact the outer walls of the pores, and the fine particles and the substrate 1804 are bonded, The coating layer 1805 was formed by closing the pores starting from the contact and junction sites.

(Example 13)

Y ₂ O ₃ (yttrium oxide) or α-Al ₂ O ₃ is used as fine particles, and the substrate for forming the structure is masked with cellophane tape (Scotch tape) and polyimide tape (Kapton (registered trademark) tape), , An example in which a structure is formed on a surface including a base material and the above-described type of tape will be described. FIG. 31(a) shows the result of using cellophane tape for masking, and FIG. 31(b) shows the result of using polyimide tape for masking. The heat resistance of polyimide tape is about 260°C, and that of cellophane tape is about 100°C. When forming a structure according to an embodiment of the present invention by using Y ₂ O ₃ (yttrium oxide) as the fine particles and slide glass as the substrate, when plasma is generated using helium gas, as shown in FIG. 31 (a) Under the condition of forming the coating portion 1905a on the slide glass as the base material, no heat damage was observed on the cellophane tape 1921a. In addition, when forming a structure according to an embodiment of the present invention by using α-Al ₂ O ₃ fine particles and SUS304 as a substrate, when plasma is generated using argon gas, as shown in FIG. 31 (b) , there is no thermal damage to the polyimide tape 1921b under the condition of forming the coating portion 1905b on SUS304 as a base material. Even with glass or SUS304 as the base material, corrosion, cracks, fractures, etc. are not observed. When forming the structure according to an embodiment of the present invention, an active region of the surface layer of fine particles is created in the aerosol supply path or inside the nozzle, which becomes a high energy region by plasma. At this time, since the temperature of the plasma flame reaching the substrate is low, the masking tape and the substrate were not damaged. Further, since the fine particles having an active region fly through the plasma flame and reach the substrate, the generated active region can be maintained and a structure can be formed. Therefore, in the present invention, heat and physical damage to the substrate are suppressed. In Fig. 31(b), a coating portion 1905b is also formed on the polyimide tape. When forming the structure according to an embodiment of the present invention, a resin or the like that is weak to heat may be used as a base material, and the structure may be directly formed on the above-described base material without pretreatment or the like.

(Example 14)

An example in which a structure according to the present invention is formed using α-Al ₂ O ₃ as fine particles and a SUS304 substrate 3004 having vertex angles of 30°, 60°, 90°, and 120° as the substrate This will be explained (Fig. 32(a) to Fig. 32(e)). In addition, an example in which a structure according to an embodiment of the present invention is formed using a SUS304 substrate 3014 having a curved shape (radius of curvature R = 25 mm) will be described (FIG. 32(f)). Argon gas was used as a type of gas that aerosolizes and supplies and conveys the fine particles, generates non-equilibrium plasma that activates the surface layer of the fine particles at a temperature below the melting point, and accelerates and ejects the fine particles that act as an impact force to the substrate. The high-frequency input power for generating non-equilibrium plasma was 0.5 to 2 kW. The supply amount of argon gas was set to 20 L/min from 5 L/min.

32(a) to 32(f) show a structure according to an embodiment of the present invention formed under the above conditions. In the conventional method, the coating portion is peeled off from the apex (for example, the portion indicated by the arrow in Fig. 32(a)), but in the structure of Example 14, the coating portion 3005 is not peeled off even at the apex portion serving as the end portion. , good adhesion to the substrate 3004 was exhibited. In the conventional method, it is peeled off from the place where uneven stress acts on the curved surface, but the structure of Example 14 shows good adhesion to the base material 3014 without peeling of the coating part 3015. 32(b) is a cross-sectional image of a portion surrounded by a circle in FIG. 32(a) observed with FE-SEM. The end of the substrate 3004 is actually a flat portion of about 80 μm, but the coating portion 3005 and the substrate 3004 are bonded with excellent adhesion, and a dense coating portion 3005 with a thickness of about 50 μm is formed on the cross section. is formed

(Example 15)

An example in which a structure according to an embodiment of the present invention is formed using α-Al ₂ O ₃ as fine particles and a ceramic porous substrate having an average pore diameter of 20 μm as a substrate will be described. Argon and helium gases are used as gases for aerosolizing and supplying and transporting fine particles, generating non-equilibrium plasma that activates the surface layer of fine particles at a temperature below the melting point, and accelerating and ejecting particles that act as an impact force on the substrate. did The high-frequency input power for generating non-equilibrium plasma was set from 0.5 to 2 kW. The supply amount of argon and helium gas was set to 20 L/min from 5 L/min. The hardness of the structure was measured using a dynamic hardness tester equipped with a Vickers indenter (SHIMADZU DUH-211).

33 is a photograph of a structure formed on a substrate. 34(a) is an image of the fracture surface of the structure observed by FE-SEM. Fig. 34(b) is an enlarged observation image of the vicinity of the substrate interface 3114 in Fig. 34(a), and Fig. 34(c) is an enlarged observation image of the vicinity of the surface layer 3113 of Fig. 34(a). In the case of forming a structure 3100 having an enclosing portion 3105 having an inclined structure as shown in FIG. 34 (a), the ratio of the activation energy to the kinetic energy of the particulates of the present invention is increased as the surface layer of the structure increases. By applying energy to the fine particles, the compressive stress of the bonding region of the fine particles in the structure 3100 is increased to the level of the surface layer. As a result, the structure 3100 having a high-density surface layer can be formed from the low-density substrate. The deformation of fine particles in the structure 3100 is smaller near the substrate interface (3114) and larger near the surface layer (3113), and the average crystal diameter of the fine particles in the structure 3100 is larger near the substrate interface (3114) near the surface layer ( 3113), the smaller it is. As a result, the structure 3100 of Example 15 exhibits a Vickers hardness of Hv300 near the substrate interface, and has an Hv1000 as the Vickers hardness increases toward the surface layer.

Here, as for the gradient structure 3100, the particle size distribution of the raw material fine particles, the average crystallite size distribution among the fine particles, and the distribution of the ratio of the short side/long side of the fine particles due to residual compressive stress, etc. ) is the structure of the surface layer. As shown in FIG. 35, the particles 3121 of the enclosing portion 3105 are composed of crystallites 3122, and the surface of the particles 3121 has an active region 3123 including an amorphous phase. At this time, the average crystallite size of the fine particles 3121 near the substrate 3104 is larger than the average crystallite size of the fine particles 3121 near the surface layer 3113 (upper layer side of the coated portion) of the coating portion 3105 . Further, the value of the short side/long side representing the deformation of the particle 3121 is smaller for the particle 3121 near the surface layer 3113 of the coating portion 3105 than for the particle 3121 near the substrate.

The novelty and inventive step of the structure can be confirmed from the above examples.

A brittle material structure according to an embodiment of the present invention can be applied to members related to semiconductor manufacturing equipment, environmental cleaning members, members related to automobiles, fuel cells, gas turbines, and general brittle material coatings.

10: ultra-fine particle structure forming device for plasma sources, 101: brittle material crosslinked structure region, 102: brittle material particles, 103: voids, 104: crosslinked structure, 105: brittle material particles, 106: brittle material particles, 107: amorphous structure 111: deposition chamber, 112: nozzle, 113: coil, 114: vacuum pipe, 115: vacuum pump, 116: aerosol generator, 117: transfer pipe, 118: pressure gauge, 119: substrate, 120: brittle material particle, 121: surface activated ultrafine particle, 122: brittle material structure, 201: brittle material particle, 202: 3-dimensional network, 301: alumina particle, 302: space, 303a: particle outermost surface, 303b: particle outermost surface Surface, 1001: brittle material structure, 1002: base material, 1010: single crystal fine particle, 1013: active region, 1021: fine particle, 1021a: fine particle, 1021b: fine particle, 1022: crystallite, 1023: active region, 1030: agglomerated powder, 1031: Raw material fine particles, 1031: polycrystalline fine particles, 1032: crystallites, 1033: active area, 1040: fine particles, 1041: raw material fine particles, 1044: active area formed by impact grinding, 1045: inactive area, 1050: fine particle, 1053: active area, 1054: active region formed by impact grinding, 1080: plasma, 1100: structure, 1101: fine particle, 1101a: fine particle, 1101b: fine particle, 1102: crystallite, 1103: active region, 1104: substrate, 1200: structure, 1201: fine particle , 1201a: fine particle, 1201b: fine particle, 1202: crystallite, 1203: active region, 1204: base material, 1205: coating portion, 1206: crystallite, 1211: surface layer, 1212: fine particle surface layer, 1300: structure, 1301: fine particle, 1302: 1303: active region, 1304: substrate, 1307: voids, 1501: raw material fine particles, 1600: structure, 1604: substrate, 1 605 coating layer, 1700 structure, 1704 substrate, 1705 coating layer, 1800 structure, 1804 substrate, 1805 coating layer, 1905a coating portion, 1905b coating portion, 1921a cellophane tape, 1921b polyimide tape, 2000 : structure manufacturing equipment, 2101: plasma generating gas cylinder, 2102: gas transport pipe, 2103: aerosol generator, 2104: aerosol conveying pipe, 2105: grinder, 2106: aerosol conveying pipe, 2107: structure manufacturing unit, 2108: plasma generation 2109: plasma generator, 2110: nozzle, 2111: substrate, 2112: step, 2113: vacuum pump, 2301: raw material particle, 2302: particle, 2303: active region, 2305: coating layer, 2307: structure, 3004: substrate , 3005: coated portion, 3014: substrate, 3015: coated portion, 3100: inclined structure, (3100): structure, 3104: substrate, 3105: coated portion, 3113: surface layer vicinity, 3114: substrate interface vicinity, 3121: fine particles, 3122: determinant; 3123: active region

Claims (19)

A structure having a brittle particle aggregate having a plurality of brittle particles,
The brittle particles are made of a material having a crystal structure selected from the group consisting of ceramics, intermetallic compounds, high molecular polymer materials, and semiconductors,
In the aggregate of brittle particles, the brittle particles disposed adjacent to each other and having a brittle material region around the brittle particles are crosslinked by the brittle material region to bind the brittle particles and prevent the brittle particles from moving. a brittle material cross-linked structure region,
The brittle particle includes a plurality of crystallites disposed inside the brittle particle and in which crystals constituting the brittle particle are refined, and the brittle material region covering the surface of the brittle particle,
The thickness of the brittle material region is 100 nm or less,
The brittle material crosslinked structure region has a shape along each surface of the brittle particle,
The brittle particles have crystallites having a crystallite size of 1 nm or more and 300 nm or less,
The structure, characterized in that the structure has a compressive residual stress.
The method of claim 1,
The structure characterized in that the brittle material crosslinked structure region has a three-dimensional network structure between the brittle particles.
The method of claim 1,
The structure, characterized in that the brittle material cross-linked structure region is amorphous.
delete The method of claim 1,
The structure characterized in that the brittle material crosslinked structure region has a void.
delete The method of claim 1,
The structure characterized in that the brittle material crosslinked structure region is composed of the same element as the constituent element of the brittle particles.
The method of claim 1,
Structure, characterized in that the size of the brittle particles is less than 5㎛.
The method of claim 1,
A structure, characterized in that the ratio of the hardness of the structure to the hardness of the brittle particles is 0.1 or more and less than 1.
A laminated structure in which the structure according to any one of claims 1 to 3, 5, and 7 to 9 is disposed on a substrate.
The method of claim 10,
The brittle particle is a laminated structure having a flat shape perpendicular to the substrate.
The method of claim 10,
A laminated structure characterized in that the substrate is a porous body.
delete The method of claim 11,
The laminated structure, characterized in that 0.02 < internal compressive stress / Vickers hardness.
The method of claim 11,
A laminated structure characterized in that the value of the short side/long side of the brittle particles is the value of the brittle particles near the interface of the substrate > the value of the brittle particles near the surface layer of the laminated structure.
The method of claim 11,
The laminated structure is characterized in that the laminated structure has an insulation withstand voltage of 20 kV/mm or more.
Supplying a carrier and plasma generating gas to aerosolize brittle particles of a raw material composed of a material having a crystal structure selected from the group consisting of ceramics, intermetallic compounds, high molecular polymer materials and semiconductors;
Among the brittle particles of the raw material, the agglomerated particles in which the primary particles are agglomerated are pulverized into primary particles,
Under reduced pressure, using nonthermal equilibrium plasma at a temperature below the melting point of the primary particles, while suppressing the central portion of the brittle particles to a phase transformation temperature or less, the surface of the primary particles is electronically excited to activating the surface to create an active area;
A method for manufacturing a laminated structure characterized by ejecting the primary particles having a plurality of the active regions onto a substrate and bonding the primary particles having a plurality of the active regions through the active regions.
The method of claim 17
The manufacturing method of the laminated structure characterized by forming an active region on the surface of the primary particle by the impact crushing effect of the primary particle and the thermal effect of the plasma.
An aerosol generator, a grinder, a vacuum pump, a plasma generator, and a nozzle connected to the plasma generator,
The aerosol generator supplied with conveying and plasma generating gas aerosolizes brittle particles of a raw material composed of a material having a crystal structure selected from the group consisting of ceramics, intermetallic compounds, high molecular polymer materials and semiconductors;
The pulverizer is provided in front of the plasma generating device, and the pulverizer pulverizes agglomerated particles in which primary particles among the brittle particles of the raw material transported from the aerosol generator are agglomerated,
While conveying to the plasma generator, the surfaces of the pulverized primary particles are suppressed to a temperature below the melting point of the primary particles at a temperature below the melting point of the primary particles using nonthermal equilibrium plasma, while suppressing the central portion of the brittle particles to below the phase transformation temperature. , Electronically exciting and activating the surface of the primary particle to create an active region,
The manufacturing apparatus for a laminated structure characterized by ejecting the primary particles having a plurality of the active regions from the nozzle.

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